DK164860B - ANALOGY PROCEDURE FOR PREPARING BENZOXAZIN-2-ONER - Google Patents

Abstract

This invention is directed to novel benzoxazin-2-ones of the formula <IMAGE> (I) wherein A is a sulfur atom or an SO, SO2, R-N=S, or R-N=SO2 group where R is a hydrogen atom or an acyl group; D is an alkylene group; R1 is an alkyl, phenylalkyl, cycloalkyl, or phenyl group; R4 is a hydrogen atom or an alkyl group; R5 is a hydrogen or halogen atom or a nitro or alkyl group; and R6 is a hydrogen or halogen atom or an alkyl group, having valuable pharmacological properties, particularly an antithrombotic activity. The compounds of Formula I may be prepared by the methods used for analogous compounds.

Description

DK 164860 B

Published European Patent Application No. 3,771 discloses carbostyril and oxindole derivatives which, in addition to a positive inotropic effect, exhibit in particular antithrombotic properties.

It has now been found that novel benzoxazin-2-ones of the general formula I: R R9 Rt vi * R6 \ wherein A is a sulfur atom, an SO, S00, RN = S group, or 15 1 RN = SO group in which R is a hydrogen atom, a straight chain alkanoyl group having 1-9 carbon atoms, a pivaloyl group, a benzoyl group optionally substituted with a fluoro, chloro or bromine atom or with a methyl, An ethyl, isopropyl, t-butyl or acetoxy group, a benzoyl group substituted with two fluorine atoms, two chlorine atoms or two or three methyl groups, a phenylsulfonyl group optionally substituted by a methyl group or a fluorine, chlorine or bromine atom, a naphthoyl, thenoyl, pyridinoyl, hydroxysulfonyl, methanesulfonyl, ethanol sulfonyl, pentamethylphenylsulfonyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, benzyloxycarbonyl, benzyloxycarbonyl, or dimethylamino carbonyl group, D is a straight or branched alkylene is a group optionally substituted with a phenyl group, alkyl group substituted alkyl group having 1-3 carbon atoms.

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atom or a phenyl group, the above-mentioned phenyl nucleus being substituted in each case by an alkyl group having 1-4 carbon atoms, a halogen atom, an alkoxy group having 1-3 carbon atoms, a hydroxy, cyclohexyl or phenyl group, an amino group or the like. an alkanoylamino group having 1-3 carbon atoms; an alkyl group of 4-8 carbon atoms, a cycloalkyl group of 3-7 carbon atoms, one of alkyl groups of 1-4 carbon atoms, alkoxy groups of 1-3 carbon atoms and / or 10 halogen atoms, di- or trisubstituted phenyl group or mono- or disubstituted hydroxyphenyl or aminophenyl group, whereby the substituents on the phenyl nucleus may in each case be the same or different, optionally substituted with one or two methyl groups, pyridyl or pyriminidyl group, a pyridyl-N-oxide, ethylpyridyl, ethylpyrimidinyl, propylpyrimidinyl, diethylpyrimidinyl, pyrazinyl, pyridazinyl, pyrazolyl, imidazolyl, triazolyl, indolyl, indazolyl, quinolyl, isoquinolyl, quinazolinyl, benzimidazolyl or benzthiazolyl group, R 2 and R are hydrogen atoms, phenyl groups, alkyl groups of 1 to 6 carbon atoms or cycloalkyl groups of 3 to 7 carbon atoms, R 4 is a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, R 5 is a hydrogen or halogen atom, a nitro or alkyl group of 1 to 3 carbon atoms, and * 6 is a hydrogen or halogen atom or an alkyl group 30 of 1 to 3 carbon atoms, exhibit valuable pharmacological properties, especially superior antithrombotic effects.

Accordingly, the invention relates to an analogous process for the preparation of the above-defined benzoxazin-2-ones of formula I; the process is peculiar to the characterizing part of the claim.

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For the meanings mentioned in the definitions of groups A, D and to R6 above, e.g. for A is a sulfur atom, a sulfoxide, sulfonyl, sulf imino, N-formyl-sulfimino, N-acetyl-sulfimino, N-propionyl-sulf imino, N-pi valoyl-sulf imino, , N-pentanoyl-sulf imino-, N-hexanoyl-sulf imino-, N -heptanoy-1-sulf imino-, N-octanoy-1-sulfin imino-, N-nonanoy 1-sulf imino-, N-methoxyacetyl-sulf imi no-, N-methoxypropionyl-sulfimino-, N-benzoyl-ΙΟ-sulfimino-, N-fluorobenzoyl-sulfimino-, N-chlorobenzoyl-sulfimino-, N-bromobenzoyl-sulfimino-, N-methylbenzoyl-sulfimino-, N -ethyl-benzoyl-sulf-imino-, N-isopropylbenzoyl-sulfimino-, N-tert. butyl benzoyl 1-sulf imino-, N-difluorobenzoyl-sulf-imino-, N-dichlorobenzoyl-sulf imino-, N-dimethylbenzoyl-sulf imino-, N-trimethylbenzoyl-sulf imino-, N-naphthoy-1 sulf imino-, N-pyridinoyl-sulf-imino-, N-thenoyl-sulf imino-, N-acetoxy-benzoyl-sulfimino-, N-hydroxysulfonyl-sulfimino-, N-methanesulfonyl-sulfimino-, N-ethanesulfonyl -sulfimino, N-phenylsulfonyl-sulfimino, N-methylphenyl-sulfonyl-sulfimino, N-fluorophenyl-sulfonyl-sulf-imino-, N-chlorophenylsulfonyl-sulfimino, N-bromo-phenylsulfonyl-s ul of imino, N-pentamethylphenylsulfonylsulfimino-, N-naphthylsulfonylsulfimino-, N-methoxycarbonylsulfimino-, N-ethoxycarbonylsulfimino-, N-propoxycarbonylsulfimino-, N-isopropoxycarbonyl -sulf imino-, N-benzyloxycarbonylsulfimino-, N-aminocarbonylsulfimino-, N-methylethylcarbonylsulfimino-, N-dimethylaminocarbonylsulfimino-, sulfoxymino-, N-formylsulfoxy- mino-, N-acetyl-sulfoxymino, N-propionyl-sulfoxymino, N-pivaloyl-sulfoxymino, N-pentanoyl-sulfox imino, N-hexanoyl-sulfoxymino, N-heptanoyl-sulfoxymino, N-nonanoyl-sulfoxymino, N-methoxyacetyl-sulfoxymino, N-methoxypropionyl-sulfoxymino, N-benzoyl-sulfoxymino, N-fluoro-benzoyl 1-sulfoxymino-, N-chlorobenzoyl-sulfoxime-4

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no, N-bromobenzoyl sulfoxymino, N-methylbenzoyl sulfoxymino, N-ethylbenzoyl sulfoxymino, N-isopropylbenzoyl sulfoxymino, N-tert-butyl benzoyl sulfoxymino, N-difluorobenzoyl sulfoxymino , N-dichlorobenzoyl sulfoxymino, N-dimethylbenzoyl sulfoxymino, N-trimethylbenzoyl sulfoxymino, N-naphthoyl sulfoxymino, N-pyridinoyl sulfoxymino, N-thenoyl sulfoxymino, N-acetoxy -benzoyl-sulfoxymino-, N-hydroxy-sulfoxymino-, N-methanesulfonyl-sulfoxymino-, N-ethanesulfonylsulfoxymino-, N-phenylsulfonylsulfonylsulfoxymino-, N-methylphenylsulfonylsulfoxymino-, N-fluorophenylsulfonylsulfonylsulfonyl , N-chlorophenylsulfonylsulfoxymino, N-bromophenylsulfonylsulfoxymino, N-pentamethylphenylsulfoxymino, N-naphthylsulfonylsulfoxymino, N-methoxycarbonylsulfoxymino, N-ethoxycarbonylsulfoxymino -sulfoxymino, N-isopropoxy-carbonyl-sulfoxymino, N-benzyloxycarbonyl-sulfoxy-amino, N-aminocarbonyl-sulfoxymino, N-methylaminocarbonyl-sulfoxymino or N-dimethyl minocarbonylsulfoxymino group, for D an ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, 1-methylethylene, 2-methylethylene, 1- methyl-n-propylene, 2-methyl-n-propylene, 3-methyl-n-propylene, 1-methyl-n-butylene, 2-methyl-n-butylene, 3-methyl-n -butylene, 4-methyl-n-butylene, 1-methyl-n-pentylene, 2-methyl-n-pentylene, 3-methyl-n-pentylene, 4-methyl-n-pentylene , 5-methyl-n-pentylene, 1,1-dimethylethylene, 1,2-dimethylethylene, 2,2-dimethylethylene, 1,1-dimethyl-n-propylene, 2, 2-dimethyl-n-propylene, 3,3-dimethyl-n-propylene, 1,2-dimethyl-n-propylene, 1,3-dimethyl-n-propylene, 1,1-35 dimethyl -n-butylene, 2,2-dimethyl-n-butylene, 3,3-dimethyl-n-butylene, 4,4-dimethyl-n-butylene,

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1,2-dimethyl-n-butylene, 1,3-dimethyl-n-butylene, 1,4-dimethyl-n-butylene, 2,3-dimethyl-n-butylene, 1-ethylethylene , 2-ethyl-ethylene, 1-ethyl-n-propylene, 2-ethyl-n-propylene, 3-ethyl-n-propylene, 1-ethyl-n-butylene, 2-ethyl -n-butylene-, 3-ethyl-n-butylene-, 4-ethyl-n-butylene-, 1-methyl-2-ethyl-ethylene-, 1-methyl-2-ethyl-n-propylene-, 1 -methyl-3-ethyl-n-propylene, 1-methyl-2-propyl-ethylene, 1-propyl-ethylene, 1-butyl-ethylene, or 1-propyl-n-propylene group, for R 1 and methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methyl-propyl, 2-methyl-propyl, tert. butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1-ethyl-n-propyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, benzyl, 1-phenylethyl, 2-phenyl-ethyl, 1-phenyl-propyl, 3-phenylpropyl, fluorobenzyl, chlorobenzyl, bromobenzyl -, methylbenzyl, isopropylbenzyl, methoxybenzyl, ethoxybenzyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, fluorophenyl, chlorophenyl, bromophenyl, methylphenyl -, isopropylphenyl, tert.butylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, n-propoxyphenyl, formylaminophenyl, acetylaminophenyl, propionylaminophenyl, cyclohexylphenyl, biphenyl, biphenyl , dichlorophenyl, dibromophenyl, dimethoxyphenyl, methoxy-chlorophenyl, methoxy-bromophenyl, dimethylphenyl, methylethylphenyl, diethylphenyl, methyl tert, butylphenyl, methyl chlorophenyl, methyl bromophenyl, tert.butyl bromo-phenyl, trimethylphenyl, dichloro-aminophenyl, dibromo-aminophenyl, dimeth γ1-aminophenyl, dichloro-hydroxyphenyl, dibromo-hydroxyphenyl, dimethyl-hydroxyphenyl, di-tert-butyl-hydroxyphenyl, trimethoxyphenyl, pyridyl, pyridyl-N-6

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oxide, methyl pyridyl, ethyl pyridyl, dimethyl pyridyl, pyrimidinyl, methyl pyrimidinyl, ethyl pyrimidinyl, propyl pyrimidinyl, dimethyl pyrimidinyl, diethyl pyrimidinyl, pyrazide 5, nyl, pyridazinyl, pyrazolyl, imidazolyl, triazolyl, indolyl, indazolyl, quinolyl, isoquinolyl, quinazolinyl, benziraidazolyl or benzthiazolyl group, for R 2 and R 3, which are the same or different, in each case, a hydrogen atom, a methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methyl-n-propyl, 2-methyl-n-propyl, tertiary compound, butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1-ethyl-n-propyl, tert-pen-15 tyl, n-hexyl, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cyclohepthyl group, for R 4 a hydrogen atom, a methyl, ethyl, n-propyl or isopropyl group, for R5 is a hydrogen, fluoro, chloro, bromo or iodo atom, a nitro, methyl, ethyl, n-propyl or isopropyl group and for Rq a hydrogen, fluoro, chloro or bromine atom, a methyl, ethyl, n-propyl or isopropyl group 25 under consideration.

Preferred compounds of the invention are those in which A is a sulfur atom, an SO, SO 2 -, RN = S or RN- = SO group, wherein R is a hydrogen atom, optionally substituted with a methyl group of benzoyl. - or phenylsulfonyl group, an acetyl or propionyl group, D is a straight chain alkylene group of 2 to 6 carbon atoms, R 1 is an alkyl group of 1 to 8 carbon atoms, a cyclohexyl, benzyl, pyridyl, pyridyl N oxide, 2-benz-thiazolyl or 1,2,4-triazol-3-yl group, optionally substituted with one or two methyl groups 2-7

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pyrimidinyl group, one optionally having an alkyl group having 1 to 4 carbon atoms, one having a hydroxy, methoxy, cyclohexyl, phenyl or acetylamino group, a fluoro, chloro or bromine atom substituted phenyl group, a 5 with chloro or bromine atom , methyl or methoxy groups disubstituted phenyl group, wherein the substituents in the phenyl nucleus may be the same or different, or one having two alkyl groups each having 1 to 4 carbon atoms, two chloro or bromine atoms substituted 10 aminophenyl or hydroxyphenyl group, R 2 and R 3, which may be the same or different are hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, phenyl or cyclohexyl groups, R 4 is a hydrogen atom or a methyl group, R 5 is a hydrogen, fluoro, chloro or bromine atom, a nitro, methyl - or ethyl group, and R 5 is a hydrogen, chlorine or bromine atom, a methyl or ethyl group, especially however the compounds in which the -ODA-R 1 group is in the 6-position.

Particularly preferred compounds of the invention are the compounds of the general formula Ia 20 1 I.

R6 b 30 wherein A is a SO-, SO2 * · H-N = SO-, CH3CO-N = SO- and CH3-CgH2 - SO2 ~ N = SO group, D is an n-butylene group, 8

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R 1 is an optionally substituted phenyl group with a fluorine, chlorine or bromine atom, a methyl, hydroxy, methoxy, cyclohexyl, phenyl or acetamino group, a chloro or bromine atom, methyl or methoxy groups disubstituted phenyl group wherein the substituents in the phenyl nucleus may be the same or different, a 4-amino-3,5-dibromo-phenyl, a 3,5-di-tert-butyl 1-4-hydroxy-phenyl or pyridyl group, R 2 and R 3, which may be the same or different, are each a 1 g hydrogen atom or a methyl group, R 5 is a hydrogen, chlorine or bromine atom, a nitro or methyl group, and

Rg is a hydrogen, chlorine or bromine atom or a methyl group.

According to the invention, the novel compounds are prepared as mentioned by:

a) Reaction of a hydroxy compound of general formula II

- vk "t 1> 0

Kc 6 R / 25 4 wherein R2 to Rg are as previously defined, or salts thereof with inorganic or tertiary organic bases,

2Q having a compound of general formula III

Z - D - A - Ri III

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wherein A, D and R 1 are as previously defined and Z is a nucleophilic leaving group such as a halogen atom or a sulfonic acid ester group, e.g. a chlorine, bromine or iodine atom, a p-toluenesulfonyloxy or methanesulfonyloxy group.

The reaction is conveniently carried out in a suitable solvent or solvent mixture such as methanol, ethanol, dioxane, tetrahydrofuran, chloroform or toluene, but preferably in an anhydrous aprotic solvent such as acetone, dimethylformamide or dimethylsulfoxide, optionally in the presence of an alkali or an alkali or an alkali alcoholate such as sodium carbonate, potassium carbonyl, sodium hydroxide or sodium ethylate at temperatures between 0 ° C and the boiling point of the solvent used, e.g. at temperatures between 0 and 100 ° C, but preferably at temperatures between 10 and 80 ° C. However, the reaction can also be carried out without solvent.

B) For the preparation of compounds of the general formula I wherein A is a SO, SO 2 or R-N = SO group:

Oxidation of a compound of general formula IV

25 R-H, R, 30 Rc R, O 'wherein

R 1 to R 5 and D have the previous definitions, and A 1 is a sulfur atom, an SO or R-N = S group, wherein R 35 is as previously defined.

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The oxidation is preferably carried out in a solvent or solvent mixture, e.g. in water, water / pyridine, ethanol, methanol, acetone, glacial acetic acid, formic acid, dilute sulfuric acid or trifluoroacetic acid, depending on the oxidizing agent used, suitably at temperatures between -80 and 100 ° C.

For the preparation of compounds of general formula I wherein R is an SO or R-N = SO group, the oxidation is conveniently carried out with an equivalent of the oxidizing agent used, e.g. with hydrogen peroxide in glacial acetic acid or formic acid at 0 to 20 ° C or in acetone at 0 to 60 ° C, with a peracid such as permyric acid or m-chloro-perbenzoic acid in glacial acetic acid or trifluoroacetic acid at 0 to 20 ° C, with sodium metaperiodate in aqueous methanol or ethanol at 15 to 25 ° C, with N-bromo-succinimide in ethanol at 10 to 50 ° C, with tert.butyl hypochlorite in methanol at -80 to -30 ° C, with iodobenzene dichloride in water pyridine at 0 to 20 ° C, with chromic acid in glacial acetic acid or in acetone at 0 to 20 ° C, and with sulfuryl chloride in methylene chloride at -70 ° C, the resulting thioether-chloro complex being suitably hydrolyzed with aqueous ethanol.

To prepare compounds of the general formula I wherein A is a SO 2 group, the oxidation is conveniently carried out with one or two or more equivalents of the oxidizing agent used, e.g. with hydrogen peroxide in glacial acetic acid or in formic acid 30 at 20 to 100 ° C or in acetone at 0 to 60 ° C, with a peracid such as permyric acid or m-chloroperbenzoic acid in glacial acetic acid, trifluoroacetic acid or chloro-11

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form at temperatures between 0 and 50 ° C, with nitric acid in glacial acetic acid at 0 to 20 ° C / with chromic acid or potassium permanganate in glacial acetic acid, water / sulfuric acid or in acetone at 0 to 20 ° C. Accordingly, if A is in a compound of the above general formula IV a sulfur atom, the reaction is preferably carried out with two or more equivalents of the oxidizing agent in question and quite similarly with at least one equivalent if A is an SO group.

C) For the preparation of compounds of the general formula I wherein A is a sulfur atom or a SO 2 group: a compound of the general formula V is reacted

r, r2 r3 20 4 wherein

D and R 2 to R 9 are defined as before and X is a nucleophilic leaving group such as a halogen atom or a sulfonic acid ester residue, e.g. a chlorine, bromine or iodine atom, a p-toluenesulfonyloxy or methanesulfonyloxy group, having a compound of the general formula VI

Y - Ri VI

Wherein R is as previously defined and Y is a MeSO 2 group wherein Me is an alkali or alkaline earth / 2 metal atom such as sodium, potassium or calcium / 2 atom or a mercapto group.

The reaction is conveniently carried out in a suitable solvent or solvent mixture such as dioxane, tetrahydrofuran, chloroform or toluene.

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one, however preferably in an anhydrous aprotic solvent such as acetone, dimethylformamide or dimethyl sulfoxide, optionally in the presence of an alkali base such as sodium carbonate, potassium carbonate or sodium hydroxide at temperatures between 0 ° C and the boiling temperature of the solvent used, e.g. . at temperatures between 0 and 100 ° C, but preferably at temperatures between 10 and 50 ° C. However, the reaction can also be carried out without solvent.

D) For the preparation of compounds of general formula I wherein A is an H-N = SO group:

A sulfoxide of the general formula VII is reacted

R1 - SO - D - 0 - j | _ 0 will; % 20 wherein D and R 1 to R 9 are defined as before, with optionally formed nitrogen hydrogen acid in the reaction mixture.

The reaction is conveniently carried out in a solvent or solvent mixture such as methylene chloride, dimethylformamide or tetrahydrofuran at temperatures between 0 and 40 ° C, preferably at temperatures between 10 and 35 ° C. Particularly advantageously, the reaction is carried out with an alkali metal, e.g. sodium azide and polyphosphoric acid as solvent.

e) For the preparation of compounds of general formula I wherein A is an H-N = SO group:

A sulfoxide of the general formula VII is reacted

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R ftp ft-,

Vy ^ R., - SO - D - C - I °

5 ^ Λκ ^ 0 VII

Rfi 6 R4 wherein

D and R 1 to R 9 are defined as before, with a compound of the general formula VIII

H2N - 0 - X - r VIII

wherein X is a carbonyl or sulfonyl group and R 7 is an aryl substituted aryl group such as a 2,4,6-trimethylphenyl or 2,4,6-triisopropylphenyl group.

The reaction is conveniently carried out in a solvent or solvent mixture such as methylene chloride, chloroform, dimethylformamide, tetrahydrofuran or dioxane at temperatures between 0 and 50 ° C, but preferably at temperatures between 5 and 40 ° C, and optionally in the presence of a catalytic amount. acid such as p-toluenesulfonic acid. However, reaction 25 is carried out particularly advantageously in that a compound of general formula VIII is used without its prior isolation or prepared in the reaction mixture.

f) For the preparation of a compound of general formula I wherein R is not a hydrogen atom:

A compound of the general formula IX is acylated

R, R,

VSX

"R.-A" -D-0-- I

35 1 R6 r4 14

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wherein D and R 1 to R 9 are defined as before and A "is an H-N = S or H-N = SO group.

The reaction is conveniently carried out in a solvent or solvent mixture such as water, methylene chloride, chloroform, ether, tetrahydrofuran, dioxane or dimethylformamide with a suitable acylating agent, e.g. with an acid in the presence of an agent which activates the acid or is water-sucking such as thionyl chloride, with its anhydrides such as acetic acid ethyl hybride, with its esters such as p-toluenesulfonic acid ethyl ester or carbonic acid ethyl ester, with its halides such as acetyl chloride, chloroacetic acid or -toluenesulfonic acid chloride, or with an appropriate isocyanate, whereby it may also act as a solvent, optionally in the presence of an inorganic or tertiary organic base such as sodium hydroxide, potassium carbonate, triethylamine or pyridine, whereby the latter may also act simultaneously. as a solvent at temperatures between -25 and 100 ° C, but preferably at temperatures between -10 and 80 ° C.

g) For the preparation of a compound of general formula I wherein A is an R-N = S group:

A thioether of the general formula X is reacted

D R R

R.-S-D-C-- I

30 ^ 0 r6 r, 35 wherein

R 1 to R 9 and D are as previously defined with a halogenamide of general formula XI

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Hall

R1 - N

^ H XI

5 wherein R *, other than a hydrogen atom, has the meanings previously mentioned for R and Hal is a chlorine or bromine atom or with its alkali salt and optionally subsequent hydrolysis.

The reaction is preferably carried out with an alkaline salt of a compound of the general formula XI, e.g. the sodium salt, optionally in the presence of an inorganic base such as an alkali base in a solvent or a solvent mixture such as methanol, methanol / water or ethanol, conveniently at temperatures between 0 and 80 ° C, but preferably at temperatures between 5 and 50 ° C.

The optionally subsequent hydrolysis is carried out in the presence of an acid or base, but preferably in the presence of a base such as sodium hydroxide, in a solvent or solvent mixture such as water, methanol, methanol / water or tetrahydrofuran / water at temperatures up to the used temperature. solvent boiling temperature.

H) To prepare a compound of general formula I wherein A is an H-N = S or H-N = SO group: an acyl residue is hydrolytically cleaved from a compound of general formula XII

R_ R

R “A * 1 — D — 0—: XII

> <A.> °

R

35 D * 4 16

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wherein D and R 1 to R 9 are as previously defined and A 1 is a H-N = S or H-N = SO group substituted with a hydrolytically cleavable acyl residue.

As an acyl residue, e.g. a carboxylic acid or a carbonic acid derivative is contemplated such as an acetyl, propionyl, butanoyl, benzoyl, pinanoyl, nicotinoyl, ethoxycarbonyl, aminocarbonyl or dimethylaminocarbonyl group.

The reaction is carried out in the presence of an acid or base, e.g. in the presence of hydrochloric acid, sulfuric acid, sodium hydroxide, potassium liquor or potassium carbonate in a solvent or solvent mixture such as water, methanol, water / methanol, water / ethanol or water / tetrahydrofuran at temperatures up to the boiling temperature of the solvent used, e.g. at temperatures between 50 and 90 ° C.

i) For the preparation of a compound of general formula I wherein R is not a hydrogen atom A compound of the general formula is reacted

XIII

Re / 5> fy "oh

25, XIII

R -Å "" - D-0 - H

Wherein D and R 1 to R 9 are as previously defined and A "" is a sulfur atom, an SO, SO 2, R'-N = S or R'-N = SO group, where R ' except for a hydrogen atom, have the meanings for R previously mentioned, with a carbon dioxide.

35 derivatives of general formula XIV

X - CO - X XIV

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wherein X, which may be the same or different, is in each case a nucleophilic leaving group such as a chlorine atom, a methoxy, ethoxy, benzyloxyl or imidazolyl group.

The reaction is conveniently carried out in an inert solvent such as ether, chloroform, dioxane, toluene or tetrahydrofuran / toluene at temperatures between 0 and 80 ° C, but preferably at room temperature.

If the invention provides a compound of general formula I wherein R 4 is a hydrogen atom, this can be carried out by alkylation in a corresponding compound of general formula I wherein R 4 is an alkyl group having 1 to 3 carbon atoms.

The subsequent alkylation is conveniently carried out with an alkyl halide such as methyl iodide or propyl bromide or a sulfonic acid ester such as dimethyl sulfate, preferably in the presence of a base such as sodium hydroxide or pyridine, optionally in the presence of a reaction accelerator such as tetrabutylammonium hydrogen sulfate and preferably methanol, ethanol, water, sodium hydroxide, tetrahydrofuran or dioxane at temperatures between 0 and 80 ° C, but preferably at room temperature.

Starting materials used compounds of general formulas II to XIV are partially known in the literature or can be obtained by known methods (see Examples A to 0).

Thus, e.g. a hydroxy compound of general formula II by reacting a suitable carbonyl compound with a suitable Grignard compound with subsequent reaction with phosgene and decomposing the group used as a protecting group for the hydroxy group and a compound of general formula V, by subsequent turnover of an 18

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thus obtained hydroxy-4H-3,1-benzoxazin-2-one with a suitable compound, e.g. with a suitable monohalogen or dihalogen compound. Furthermore, a compound of general formula V is also obtained by transferring the hydroxy group into a suitable compound in a nucleophilic leaving group, e.g. using thionyl chloride or methanesulfonyl chloride.

A compound of general formula III is obtained by reacting an appropriate α, ω-disubstituted alkane 10 with an appropriate mercapto compound and optionally subsequent oxidation.

A starting compound used with the general formulas IV, VII or XII is obtained by reacting an appropriate hydroxy compound of the general formula II with a suitable compound. A compound thus obtained can then be transferred by oxidation into a compound of general formula IX or XII.

A compound of general formula VIII used as starting material is obtained e.g. by reaction of an appropriate O-carbonyl or O-sulfonylacetydroxy formic acid ester with sulfuric acid and subsequent extraction after addition of a base.

For example, a compound of the general formula X used as starting material is obtained. by reacting an appropriate hydroxy or mercapto compound with an appropriate halide in the presence of a base.

A starting compound used with the general formula XI is obtained by reacting a suitable amide with a hypohalogenite, optionally in the presence of a base.

A starting material used as a compound of general formula XIII is obtained by reacting a suitable anthranilic acid ester with a suitable Grignard compound.

Further, a starting material of the general formula II thus prepared can subsequently be added at 19

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chlorination or bromination, e.g. by chlorine, sulforyl chloride or bromine is stirred in the corresponding halogen compound, optionally with nitric acid in the corresponding nitro compound.

The compounds of general formula I wherein A

is a sulfur atom or an R-N = S group, are valuable intermediates for preparing the compounds of general formula I wherein A is a SO, SO 2 or R-N = SO group.

Furthermore, the novel compounds of the general formula I have, as mentioned previously, valuable pharmacological properties, especially antithrombotic effects. They promote the synthesis of aggregation-inhibiting prostaglandins in the vessel wall. The compounds of general formula I also have an inhibitory effect on tumor metastasis. This is due to the following properties of the compounds of the invention: 1. They are platelet phosphodiesterase inhibitors known as inhibitors of tumor metastasis (H.

Gastpar, Thrombosis Research, 277-289 (1974) and K.V. Hon. Science 212, 1270-1272 (1981)).

2. The compounds inhibit primary hemostasis already at very low dosage. The adherence of thrombocytes to damaged vessels and the formation of a clean blood platelet thrombus are avoided, leading to a strong prolongation of bleeding time. This is explained by the compounds of formula I not only by a restriction of platelet function, but by a further elevated release of platelet-active PG through the vessel's endothelial cells. A confirmation of this is the absence of bleeding time extension if the prostacyclin synthesis in the endothelial cells is interrupted with the previously administered cyclooxygenase inhibitor. Thus, the compounds present an unprecedented optimal combination of two principles of action, namely the increased synthesis of platelet-acting c.AmP-elevating PGs through the vessel wall and inhibition of 20

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the degradation of the increased c.AinP through inhibition of PDE in the platelets.

According to 5 HONN (K.V. Honn, Science 212, 1270-1272 (1981)), the increase in prostaglandin activity or synthesis in the vessel wall is similarly caused by the inhibition of tumor metastasis.

Eg. the following compounds A = 6- [4- (4-chloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one, B = 6- [4- (4) -hydroxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one, C = 6- [4- (4-methoxy-phenylsulfoxymino) -butoxy] 4.4- dimethyl-4H-3,1-benzoxazin-2-one, D = 6- [4- (4-methyl-phenylsulfinyl) -butoxy] 4,4-dimethyl-4H-3,1-benzoxazin-2-one, E = 6- [4- (4-cyclohexyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one, F = 6- [4- (3,4-dichloro-2-one) phenylsulfoxymino) -butoxy] 4,4-dimethyl-4H-3,1-benzoxazin-2-one, G = 6- [4- (3-methoxy-phenylsulfoxymino) -butoxy] -4,4-di methyl 4H-3,1-benzoxazin-2-one, H = 6- [4- (4-fluoro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazine-2-one one, 6- [4- (4-bromo-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one, K = 6- (4-phenylsulfinyl-2-one) butoxy) -4H-3,1-benzoxazin-2-one, L = 6- [4- (4-bromo-phenylsulfonyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one , M = 6- [4- (4-bromo-3-methyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl 1-4H-3,1-benzoxazin-2-one, N = 6- [4- (4-methyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazine-2-one one, O = 6- [4- (3,4-dimethoxy-phenylsulfoxymino) -butoxy] -4,4- 35 dimethyl-4H-3,1-benzoxazin-2-one, P = 6- [4- (4 -amino-3,5-dibromo-phenylsulfonyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one, 21

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Q = 6- [4- (4-biphenylyl-sulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one, R = 6- [4- (3,4-biphenylyl) dimethoxy-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one, 5 S = 6- [4- (3,5-di-tert-butyl) -4-hydroxy-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one, T = 7-bromo-4,4-dimethyl-6- [ 4- (4-methyl-phenylsulfoxymino) -butoxy] -4H-3,1-benzoxazin-2-one, 10 µl = 7-chloro-4,4-dimethyl-6- [4- (4-methyl-benzoxazin-2-one) phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one and V = 7-bromo-6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy-4,4-dimethyl-4H-3 , 1-benzoxazin-2-one for their biological properties as follows: 1. PDE inhibition:

Principle: c.AMP is hydrolyzed by phosphodiesterase (PDE) from various sources, thus also from platelets to AMP. This hydrolysis is inhibited by concentration dependent concentration of PDE inhibitors.

Method:

As phosphodiesterase, the above liquid from 10,000 x g was used on human platelets which were frozen with water and thawed again.

25 ml of a mixture containing 0.1 mole / liter of trishydroxyaminomethane (pH 7.4), 3 mmol / liter of magnesium chloride, 1 mmol / liter of AMP 1 µmol / liter of ³H-cAMP (specific activity (about 10 MBq / pmol), PDE as well as the substances to be examined or water for the control were incubated for 15 minutes at 37 ° C.

The incubation was stopped by the addition of 0.5 ml of zinc sulfate (0.266 mol / liter) and 0.5 ml of barium hydroxide (0.226 mol / liter), the precipitate was centrifuged and the activity remaining in the above liquid of the unreacted 3 H-cAMP was determined. From comparison 22

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between the substance additives and the control additives, the concentration was calculated for a 50% inhibitory effect (IC50) for the individual substance: 5 Substance lc50 [iJinol / l) ter A 0.24 B 0.23 C 0.13 D 0.21 10 E 0.078 F 0.042 G 0.077 H 0.18 I 0.11 15 K 1.5 L 0.24 M 0.066 N 0.065 0 0.20 20 P 0.056 Q 0.0068 R 0.71 S 0.077 T 0.001 25 U 0.0034 V 0.0038 2. Antithrombotic effect.

Methodik.

Thrombocyte aggregation was measured according to the method of BORN and CROSS (J. Physiol. 170, 397 (1964) 9 in platelet-rich plasma from healthy subjects. To inhibit clotting, blood sodium citrate was added 3.14% in a 1:10 volume ratio.

35 Collagen-induced aggregation.

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The platelet suspension optical density reduction process is measured and recorded photometrically after addition of the aggregation triggering agent. From the slope of the density curve, the aggregation velocity is found. The point on the curve at which the greatest light permeability is available serves to calculate the "optical density".

The amount of collagen is chosen as small as possible, but so as to produce an irreversibly continuous 10 reaction curve. The well-known collagen from Hormonchemie, Munich, Germany is used.

Prior to the collagen addition, the plasma is incubated in each case for 10 minutes with the substance at 37 ° C.

From the measurements obtained a graphical calculation of a 15 EC 50 / s indicates a 50% change in the "optical density" expressed as an aggregation inhibition.

The following table contains the results found:

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Fabric ec50 [μπιοί / literj A 0.34 B 0.23 C 0.27 5 D 0.33 E 0.32 F 0.21 G 0.27 H 0.32 10 I 0.33 K 1.90 L 0 , 42 M 0.25 N 0.22 15 0 0.27 P 0.55 Q 0.25 R 2.30 S 2.20 20 T 0.069 U 0.028 V 0.044 3. Determination of bleeding time extension.

25 Note.

Both the human organism and the organism of warm-blooded animals have an ingenious mechanism to protect them from blood loss in the event of damage.

This system consists of platelets (platelets) which, by means of adhesive properties, must quickly "stop" a cardiac defect and thus cause the primary hemostasis. In addition to this pure cellular bleeding arrest mechanism, the body has a blood clotting system. In this system, plasma factors (egg whites) are brought into active form, which ultimately converts the liquid plasma ibrinogen into a solidified fibrin mass.

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The primary hemostasis system, which is essentially the thrombocytes and the clotting system, complements each other with the common goal of effectively protecting the body from blood loss.

5 In many diseases, an intact vessel system can also be used for solidification processes and clumping of platelets. The attenuation of the blood-clotting system with coumarin or heparin is known and can be readily measured by known blood-clotting studies which, during preparation, show an extension (plasma calcification time, fast determination, thrombocin time, etc.).

Since the first rapid anesthesia in the event of a lesion occurs in the platelets, the function of the platelets in determining a standardized lesion can be well determined by measuring the bleeding time. The normal bleeding time in humans is approx. 1 to 3 minutes, but it is assumed that effective platelets are present in sufficient numbers. At a normal platelet count, a prolonged bleeding time indicates a deviating platelet function. This is seen e.g. in some congenital platelet disorders.

On the other hand, if the tendency of the platelets to spontaneously clump, with the resultant 25 cartilage closures in the arterial system, with medications is prevented, the bleeding time under the influence of the drug must accordingly be prolonged by a successful platelet treatment.

Thus, for a platelet-active substance, an extension of the bleeding time and - since the plasmatic clotting system is not affected - a normal blood clotting time must be expected.

Literature: W.D. Keidel: Short-term textbook of physiology, Georg Thieme Verlag Stuttgart, 1967, page 31: Der Blutstillungsvorgang.

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To determine the bleeding time, awake mice were administered the substances to be tested at a dose of 10 mg / kg p.o. After 1 hour, the tail tip of each animal was cut approx. 0.5 mm, and the withdrawing blood was gently dipped with a filter paper at intervals of 30 seconds until the bleeding stopped. The number of blood drops thus obtained gives a measure of the bleeding time (5 animals per trial). The following figures indicate the percentage increase over 10 controls without drug administration:

Substance Bleeding time extension in _% after 1 hour A> 248 B> 263 15 C> 241 D> 250 E 46 F> 275 G> 245 20 H 46 X> 220 K 121 L> 266 M 100 25 N 63 0> 227 P 73 Q 128 R> 241 30 S> 226 T 60 U> 230 V 100 27

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4. Acute toxicity.

The acute toxicity of the substances to be tested was determined in groups of 10 mice after oral administration of a single dose (observation time: 14 days):

Substance_Orienting acute toxicity A 1000 mg (0 of 10 animals dead) B 1000 mg (0 of 10 animals dead) C 1000 mg (0 of 10 animals dead) 10 D 1000 mg (0 of 10 animals dead) E 1000 mg (0 of 10 animals dead) R 1000 mg (0 of 10 animals dead) S 1000 mg (0 of 10 animals dead) T 1000 mg (0 of 10 animals dead) U 1000 mg (0 of 10 animals dead) V_1000 mg (0 of 10 Due to their pharmacological properties, the novel compounds are suitable for the treatment and prophylaxis of thromboembolic disorders such as 20 coronary infarction, cerebral infarction, so-called transient ischaemic attacks, amaurosis fugax, for prophylaxis of arteriosclerosis and for metastasis prophylaxis.

5. Comparison of antithrombotic activity and PDE inhibition, respectively, for compounds prepared according to the invention and for closest known compounds:

The following compounds Compounds A-H and Comparative Compounds A-H 'and F "were compared as described above under points 2 and 1 in terms of antithrombotic activity and PDE inhibition.

30 'A = 6- [4- (4-Chlorophenylsulfinyl) butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-3-one (see compound A) A' = 6- [4- (4- chlorophenylsulfinyl) butoxy] -3,4-dihydrocar-bostyril (see compound I of EP-A-3,771) B = 6- [4- (4-cyclohexylphenylsulfinyl) butoxy] -4,4-dimethyl-4H-3, 1-benzoxazin-2-one (see compound E) 28

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B '= 6- [4- (4-cyclohexylphenylsulfinyl) butoxy] -3,4-dihydrocarbostyril (see Example 204 in EP-A-3,771) C = 6- (4-phenylsulfinylbutoxy) -4H-3.1 - benzoxazin-2-one (see compound K) 5 C = 6- (4-phenylsulfinylbutoxy) -3,4-dihydrocarbostyril (see compound B of EP-A-3,771) D = 6- [4- (3,4-dichlorophenylsulfoxime) ) butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one (see Example 295) D '= 6- [4- (3,4-dichlorophenylsulfoxymo) butoxy] -3,4-dihy -10 drocarbostyril (see Example 2 of EP-A-71,150) E = 6- [4- (4-Chlorophenylsulfoxime) butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one (see Example 336) E '= 6- [4- (4-Chlorophenylsulfoxime) butoxy] -3,4-dihydrocarbostyril (see Example 9 of EP-A-71,150) F = 6 - [. 4- (3.4 -dimethoxyphenylsulfoxime) butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one (see Example 332) F1 = 6- [4- (3,4-dimethoxyphenylsulfoxime) butoxy] -3,4 dihydrocarbostyril (see Example 84 of EP-A-71,150) F "= 3,3-dimethyl-5- [4- (3,4-dimethoxyphenylsulfoxymo) -butoxy] indolinone (2) (see Example 43 of EP A-71.150) G = 6- [4- (3.4 -dimethylphenylsulfoxymol) butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one (see Example 333) G1 = 3,3-dimethyl-5- [3,4-dimethylphenylsulfoxymol) butoxy] - indolinone- (2) (see Example 121 of EP-A-71,150) h = 6- [4- (3,4-dichloro-N-acetylphenylsulfoxime) butoxy] -4,4-dimethyl-4H-3,1-benzoxazine 2-one (see Example 296), and H * = 6- [4- (N-acetyl-3,4-dichlorophenylsulfoxime) butoxy] -3,4-dihydrocarbostyril (see Example 47 in EP-A-71,150)

The following results were obtained: 35 29

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Antithrombotic effect

Compound E 50 50 A 0.34 A 4.0 B 0.32 B 3.4 3.4 1.90 C 4.0 D 0.21 D 2.3 E 0.039 E 3.2 20 F 0.03 F * 3.2 F '1 0.46 G 0.027 25 G' 0.36 H 3.0 H '6.0 30 30

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PDE Inhibition

Compound IC 50 5 A 0.24 A 0.8 B 0.078 B 1.6 1.5 C 1.5 C 1.9 D 0.0042 D 0.31 E 0.016 E * 0.84 F , 0082 F '1.6 F'1 0.28 G 0.0040 25 G' 0.07 H 0.22 H1 * 0.84

For the tested compounds prepared according to the invention, both effects are seen from superior to clear superior to the corresponding known compounds.

35 31

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Conveniently, the dosage required to achieve an effective effect is 0.3 to 4 mg / kg body weight two to four times daily, preferably 0.3 to 2 mg / kg body weight. To this end, the compounds of the general formula I according to the invention may optionally be worked up in combination with other active substances together with one or more inert ordinary carriers and / or diluents, e.g. with corn starch, milk sugar, cane sugar, microcrystalline cellulose, magnesium stearate, polyvinylpyrrolidone, citric acid, tartaric acid, water, water / ethanol, water / glycerine, water / sorbit, water / polyethylene glycol, propylene glycol, cetyl stearyl alcohol, hard fat or suitable mixtures thereof, for common galenic preparations such as tablets, dragons, capsules, powders, suspensions or suppositories.

The following examples further illustrate the invention:

Preparation of starting materials

Example A

6-methoxy-4,4-dimethyl-4H-3, l-benzoxazin-2-one.

A) 2-Amino-5-methoxy-phenyl-dimethyl-carbinol.

With stirring, a solution of 261 ml (4.2 moles) of methyl iodide in 1000 ml of absolute ether was dropped to a suspension of 102 g (4.2 moles) of magnesium chips in 300 ml of absolute ether within 2.5 hours and stirred further. one hour. Then, during cooling, - in order that the temperature did not rise above 20 to 25 ° C - drop a solution of 181.2 g (1 mole) of 5-methoxy-anthranilic acid methyl ester in 1.5 liters of absolute ether.

After 1 hour of stirring, the mixture was poured into 35 32

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ammonium chloride-containing ice water, the ether phase was isolated, washed with anunonium chloride-containing water, dried over sodium sulfate and the ether distilled off.

b) 6-Methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

The residue of 2-amino-5-methoxy-phenyl-dimethyl-carbinol, after distilling off the ether, was dissolved without further purification in 1.5 liters of chloroform, 276.4 g (2 moles) of potassium carbonate added and heated to 40 ° C. To this solution, 600 ml of 2% * solution of phosgene in toluene (1.2 mol) was added dropwise over 2 hours to a temperature of the reaction mixture between 40 and 50 ° C, thereby causing any foaming . After completion of the addition, the mixture was allowed to stand overnight at room temperature.

Then 1 liter of water was added, the chloroform / two luen phase was isolated, the aqueous phase extracted several times with chloroform to which little methanol was added. The combined organic extracts were washed with water, dried over sodium sulfate and the solvent was distilled off. The crystalline residue was recrystallized from toluene / acetic acid ethyl ester = 9: 1.

Mp: 182-183 ° C.

Yield: 130 g (64% of theory relative to the 5-methoxy-anthranilic acid methyl ester used).

Similarly, the following compounds were obtained: 6-methoxy-4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one from 5-methoxy-anthranilic acid methyl ester, n-hexyl-magnesium -bromide and phosgene.

Mp: 101-103 ° C.

Yield: 70.8% of theory.

6- Methoxy-4,4-diphenyl-4H-3,1-benzoxazin-2-one from 5-methoxy-anthranilic acid methyl ester, phenylmagnesium bromide and phosgene.

Mp: 237 ° C.

Yield: 69.5% of theory.

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6-methoxy-4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one from 5-methoxy-anthranilic acid methyl ester, cyclohexylmagnesium bromide and phosgene. Mp: 269-271 ° C.

Yield: 50.4% of theory.

5-Methoxy-4-isopropyl-4H-3,1-benzoxazin-2-one from 5-methoxy-2-amino-benzaldehyde (prepared from 5-methoxy-2-nitro-benzaldehyde and Pt / H2 at 30 bar and 35 ° C), isopropylmagnesium iodide and phosgene.

Mp: 124-125 ° C.

Yield: 37.1% of theory.

6- methoxy-4-ethyl-4H-3,1-benzoxazin-2-one from 5-methoxy-2-amino-benzaldehyde, ethylmagnesium bromide and phos- • S gene.

Mp: 88-89 ° C.

Yield: 30.2% of theory.

6-Methoxy-4-phenyl-4H-3,1-benzoxazin-2-one from 5-methoxy-2-amino-benzaldehyde, phenylmagnesium bromide and phosgene.

Mp: 157-158 ° C.

Yield: 36.3% of theory.

6-Methoxy-4,4-diethyl-4H-3,1-benzoxazin-2-one from 5-methoxy-anthranilic acid methyl ester, ethylmagnesium bromide and phosgene.

Mp: 123-125 ° C.

Yield: 90.1% of theory.

6- methoxy-4-methyl-4H-3,1-benzoxazin-2-one from 5-methoxy-2-amino-benzaldehyde, methylmagnesium iodide and phosgene.

Mp: 120-121 ° C.

Yield: 20.2% of theory.

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5- Methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one from 6- methoxy-anthranilic acid methyl ester, methylmagnesium iodide and phosgene.

Mp: 139-141 ° C.

Yield: 22% of theory.

7- Methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one from 4-methoxy-anthranilic acid methyl ester, methylmagnesium iodide and phosgene.

TO mp: 119-121 ° C.

Yield: 62% of theory.

8- Methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one from 3-methoxy-anthranilic acid methyl ester, methylmagnesium iodide and phosgene.

Mp: 95-96 ° C.

Yield: 42.1% of theory.

6-Methoxy-4,4,7-trimethyl-4H-3,1-benzoxazine-2-one from 5-methoxy-4-methyl-anthranilic acid methyl ester, methyl-magnesium iodide and phosgene.

Mp: 134-135 ° C.

Yield: 45.5% of theory.

6- methoxy-4,4,8-trimethyl-4H-3,1-benzoxazin-2-one from 5-methoxy-3-methyl-anthranilic acid methyl ester, methyl-magnesium iodide and phosgene.

Mp: 218-219 ° C.

Yield: 65.8% of theory.

6- Methoxy-5,7-dichloro-4,4-dimethyl-4H-3,1-benzoxazin-2-one from 5-methoxy-4,6-dichloro-anthranilic acid methyl ester, methylmagnesium iodide and phosgene.

Mp: 203-204 ° C.

Yield: 44.0% of theory.

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6-Methoxy-5,7-dimethyl-4H-3,1-benzoxazin-2-one from 5-methoxy-4,6-dimethyl-anthranilic acid methyl ester, methylmagnesium iodide and phosgene.

Mp: 152-153 ° C.

Yield: 38.7% of theory.

Example B

6- Methoxy-4H-3,1-benzoxazin-2-one.

a) 2-Amino-5-methoxy-benzyl alcohol.

] 0 181.2 g (1 mole) of 5-methoxy-2-nitro-benzaldehyde (prepared by methylation of 2-nitro-5-hydroxy-benz-aldehyde with methyl iodide / potassium tert.butylate in dimethyl sulfoxide) were dissolved in 1/8 liter of methanol, 50 g of Raney nickel was added and hydrogenated at room temperature and 5 bar. After 10 hours, hydrogen uptake was complete. The catalyst was suctioned off and the methanol was distilled off.

b) 6-Methoxy-4H-3,1-benzoxazin-2-one.

The residue remaining after distilling off the methanol was dissolved in 1 liter of chloroform without further purification and 175 g (1.25 mole) of potassium carbonate was added.

To this suspension, 553 ml (1.05 mole) of 20% solution of phosgene in toluene was gently dropped at 50 ° C with stirring. After 2 hours of stirring at room temperature, the mixture was poured into ice water, the chloroform / toluene phase was separated and the aqueous phase extracted several times with chloroform / methanol * 5/1. The combined organic extracts were washed with water, dried over sodium sulfate and the solvent was distilled off.

The residue was purified by column chromatography (silica gel, chloroform / acetone = 19: 1). The crystals remaining after distilling off the eluent melted at 154-156 ° C.

Yield: 110.5 g (61.7% of theory).

Analogously, the following compound was obtained: 6-methoxy-7-chloro-4H-3,1-benzoxazin-2-one.

Mp: 208-210 ° C.

Yield: 38.7% of theory.

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36

Example C

6-hydroxy-4,4-dimethyl-4H-3, l-benzoxazin-2-one.

237.5 g (1.146 moles) of 6-methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one were dissolved in 2.4 liters of dry ethylene chloride and added with stirring at -30 to -40 C drop dropwise 125 ml (330.3 g = boron tribromide. After completion of addition, warmed to room temperature and allowed to stand overnight. Then, after cooling and stirring, 1 liter of 50% ethanol was added dropwise, the mixture was reduced to about 500 ml and diluted with 3 liters of water. The precipitated precipitate was aspirated and dried.

Mp: 202-204 ° C (from acetic acid ethyl ester / petroleum ether).

Yield: 223.3 g (99.8% of theory).

Analogously, the following compounds were obtained: 6-hydroxy-4H-3,1-benzoxazin-2-one.

Mp 244-245 ° C.

Yield: 78.5% of theory.

6-hydroxy-4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.

Mp: 144-146 ° C.

Yield: 92.4% of theory.

6-hydroxy-4,4-diphenyl-4H-3, l-benzoxazin-2-one.

Mp: 239 ° C (dec.).

Yield: 90.0% of theory.

6-hydroxy-4-isopropyl-4H-3,1-benzoxazin-2-one.

Mp: 215-216 ° C.

Yield: 77.6% of theory.

6-hydroxy-4-ethyl-4H-3, l-benzoxazin-2-one.

Mp: 216-218 ° C.

Yield: 68.5% of theory.

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6-hydroxy-4,4-dicyclohexy1-4H-3,1-benzoxazin-2-one.

Mp:> 280 ° C.

Yield: 97.8% of theoretical 6-hydroxy-4,4-diethyl-4H-3,1-benzoxazin-2-one.

Mp: 194-195 ° C.

Yield: 95.5% of theory.

6- hydroxy-4-methyl-4H-3,1-benzoxazin-2-one.

Mp: 226 ° C.

Yield: 75.8% of theory.

7- hydroxy ~ 4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Mp: 180-182 ° C.

Yield: 96.8% of theory.

5-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Mp: 251 ° C.

Yield: 79% of theory.

8-hydroxy ~ 4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Mp: 203-205 ° C.

Yield: 90% of theory.

6- hydroxy-4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Melting point: 174 ° C (dec.).

Yield: 94.3% of theory.

6-Hydroxy-4,4,7-trimethyl 1-4H-3,1-benzoxazin-2-one.

Mp: 150-152 ° C.

Yield: 85.8% of theory.

8-Chloro-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Mp: 196-198 ° C.

Yield: 52% of theory.

7- Chloro-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Mp: 218-219 ° C.

Yield: 97.1% of theory.

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7- Bromo-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Mp: 157-158 ° C.

Yield: 96% of theory.

8- Bromo-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Mp: 212-214 ° C.

Yield: 46.7% of theory.

7,8-dibromo-6-hydroxy-4,4-dimethyl-4H-3, l-benzoxazin-2-one.

Mp: 194-195 ° C.

Yield: 24% of theory.

6-hydroxy-7-chloro-4H-3, l-benzoxazin-2-one.

Mp: 250 ° C (dec.).

15

Yield: 96.2% of theory.

6-hydroxy-5,7-dichloro-4,4-dimethyl-4H-3, l-benzoxazin-2-one.

Mp: 215-217 ° C.

20

Yield: 88.0% of theory.

6-hydrox-5,7-dimethyl-4H-3, l-benzoxazin-2-one.

Mp: 210-211 ° C.

Yield: 70.5% of theory.

25

Example D

6- (5-Bromo-pentoxy) -4,4-dimethyl-4H-3, l-benzoxazin-2-one.

A solution of 19.3 g (0.1 mol) of 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one in 200 ml of dimethyl sulfoxide was added at room temperature 41.5 g (0, 3 moles of potassium carbonate and 92 g (0.4 moles) of 1,5-dibromo-pentane, thereby raising the temperature to 45 ° C. After 2 hours of stirring, ice water was added and extracted with chloroform. The chloroform phase was washed with water, dried over sodium sulfate and the chloroform distilled off. The residue was recrystallized from acetic acid ethyl ester / petroleum ether.

Mp: 113-115 ° C.

Yield: 26.9 g (78.6% of theory).

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Analogously, the following compounds were obtained: 6- (3-chloro-propoxy) -4-i-sopropyl-4H-3,1-benzoxazin-2-one from 6-hydroxy-4-isopropyl-4H-3,1-benzoxazine -2-one and 3-bromo-propyl chloride.

Mp: 104-105 ° C.

Yield: 68.0% of theory.

6- (3-Chloro-propoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one from 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 103-bromo-propyl chloride.

Mp: 137-138 ° C.

Yield: 71.6% of theory.

6- (6-Bromohexyloxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one from 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazine-2 -one and 1,6-dibromohexane.

Mp: 125-126 ° C.

Yield: 59.2% of theory.

6- (2-Chloroethyl) -4,4-dimethyl-4H-3,1-benzoxazin-2-one from 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazine-2-one one and benzenesulfonic acid (2-chloroethyl) ester.

Mp: 128-129 ° C.

Yield: 34.4% of theory.

25

Example E

6- (4-Acetoxy-butoxy) -4H-3,1-benzoxazin-2-one.

102 g (0.62 mole) of 6-hydroxy-4H-3,1-benzoxazin-2-one was dissolved in 1 liter of dimethyl sulfoxide and 227 30 g (1.64 mole) of potassium carbonate and 166 g (0.73 mole) were added. aceto-oxybutylbromid. The reaction mixture was stirred for 6 hours at 50 ° C and then ice water was added. The precipitate was aspirated, washed with water and dried.

Mp. 119-120 ° C.

Yield: 142.8 g (82.7% of theory).

40

DK 164860 B

Analogously, the following compounds were obtained: 6- (4-acetoxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one oil; RF value: 0.8 (silica gel plate: chloroform / ethanol = 9: 1).

Yield: 100% of theory.

6- (4-acetoxy-butoxy) -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one oil; RF value: 0.6 (silica gel plate: chloroform / ace-10 tone = 9: 1).

Yield: 100% of theory.

6- (4-acetoxy-butoxy) -4,4-diphenyl-4H-3,1-benzoxazin-2-one; oil, RF value: 0.55 (silica gel plate: chloroform / ace-tone = 9: 1).

Yield: 81% of theory.

6- (4-acetoxy-butoxy) -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.

Mp: 177-178 ° C.

Yield: 68.8% of theory.

7- (4-acetoxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one; oil, RF value: 0.5 (silica gel plate: ethylene chloride / ethanol = 9: 1).

Yield: 100% of theory.

8- (4-Acetoxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Mp: 154-158 ° C.

Yield; 100% of the theoretical.

6- (4-acetoxy-butoxy) -4,4-diethy1-4H-3,1-benzoxazin-2-one; oil, RF value: 0.38 (silica gel plate: 35 chloroform / ethanol = 19: 1).

Yield: 95% of theory.

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DK 164860 B

6- (4-aethoxy-butoxy) -4-methyl-4H-3,1-benzoxazin-2-one; oil, RF value: 0.5 (silica gel plate: chloroform / ethanol = 9: 1).

Yield: 98% of theory.

6- (4-acetoxy-butoxy) -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one; oil, RF value: 0.8 (silica gel plate: chloroform / acetone = 9: 1).

Yield: 97% of theory.

6- (4-acetoxy-butoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one; oil, RF value: 0.5 (silica gel plate: ethylene chloride / acetone = 9: 1).

Yield: 98% of theory.

15

Example F

6- (4-Hydroxy-butoxy) -4H-3,1-benzoxazin-2-one.

To a solution of 150 g (0.537 mol) of 6- (4-acetoxy-butoxy) -4H-3,1-benzoxazin-2-one in 500 ml of methanol was added dropwise with stirring at 10 to 15 ° C. 24 g (0.6 mole) of sodium hydroxide in 100 ml of water. After 1 hour of stirring at room temperature, ice water was first added and then 60 ml of glacial acetic acid. The precipitated product was suctioned off and recrystallized in water.

Mp: 133-134 ° C.

Yield: 61.5 g (48.4% of theory).

Analogously, the following compounds were obtained: 6- (4-Hydroxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazine-2-30 one.

Mp: 124 ° C.

Yield: 82.9% of theory.

6- (4-hydroxy-butoxy) -4,4-diphenyl-4H-3,1-benzoxazine-2-35 one.

Mp: 188-189 ° C.

Yield: 79% of theory.

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DK 164860 B

6- (4-hydroxy-butoxy) -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.

Mp: 105-107 ° C.

Yield: 56% of theory.

6- (4-hydroxy-butoxy) -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.

m.p .; 233-234 ° C.

Yield: 77.6% of theory.

7- (4-hydroxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Mp: 105-106 ° C.

Yield: 53.4% of theory.

8- (4-hydroxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Mp: 150-151 ° C.

Yield: 73% of theory.

6- (4-hydroxy-butoxy) -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Mp: 126-127 ° C.

Yield: 69.3% of theory.

6- (4-hydroxy-butoxy) -4-methyl-4H-3,1-benzoxazin-2-one; oil, RF value: 0.4 (silica gel plate: chloroform / ethanol = 9: 1).

Yield: 61.6% of theory.

6- (4-hydroxy-butoxy) -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one.

Mp: 140-141 ° C.

Yield: 37.8% of theory.

6- (4-hydroxy-butoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Mp: 128-129 ° C.

Yield 64.2% of theory.

5

Example G

6- (4-Chloro-butoxy) -4H-3, l-benzoxazin-2-one.

To 300 ml of thionyl chloride was added with stirring at room temperature 60 g (0.253 mol) of 6- (4-hydroxy-butoxy) -4H-3,1-benzoxazin-2-one and 5 ml of pyridine. After 2 hours of reflux, the excess thionyl chloride was distilled off in a rotary evaporator, the residue was taken up in chloroform and stirred with the same volume of ice water for 30 minutes. Then the chloroform phase was isolated, washed two more times with water, dried over sodium sulfate and the chloroform distilled off. The residue was recrystallized from toluene / diisopropyl ether = 3: 1.

Mp: 127-128 ° C.

Yield; 53 g (81.9% of theory).

Analogously, the following compounds were obtained: 6- (4-chloro-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Mp: 138-139 ° C.

Yield: 75.7% of theory.

6- (4-chloro-butoxy) -4,4-di-n-hexyl-4H-3, l-benzoxazin-2-one; oil, RF value: 0.65 (silica gel plate; chloroform / ace tone = 9: 1).

Yield: 100% of theory.

6- (4-chloro-butoxy) -4,4-diphenyl-4H-3,1-benzoxazin-2-one oil, RF value: 0.38 (silica gel plate cyclohexane / acetic acid ethyl ester = 9: 1).

35

Yield: 28.7% of theory.

44

DK 164860 B

6- (4-chloro-butoxy) -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.

Mp 231-232 ° C.

Yield: 72.8% of theory.

6- (4-Chlorobutoxy) -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Mp: 90-92 ° C.

Yield: 99.4% of theory.

6- (4-chloro-butoxy) -4-methyl-4H-3,1-benzoxazin-2-one; oil, RP value: 0.8 (silica gel plate: chloroform / ethanol = 9: 1).

Yield: 32.1% of theory.

8- (4-Chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Snip: 155-156 ° C.

Yield: 93.8% of theory.

6- (4-chloro-butoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Mp: 149-150 ° C.

Yield: 95.6% of theory.

Example H

7- (4-Methanesulfonyloxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

5.3 g (0.02 mol) of 7- (4-hydroxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one was dissolved in 20 ml of pyridine and added with stirring at 0 to 5 ° C drop 4.6 g (0.04 mole) of methanesulfonic acid chloride. After 10 minutes of stirring, ice-water / hydrochloric acid was added and the mixture extracted with chloroform. After washing the extracts with water and drying with sodium sulfate, the solvent was distilled off in vacuo. The solid residue was stirred with 35 diisopropyl ether, suctioned off and dried.

Mp: 134-136 ° C.

Yield: 6.4 g (93.3% of theory).

45 DK 16486U 8

Analogously, the following compound 6- (4-methanesulfonyloxy-butoxy) -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one was prepared.

Mp: 149-151 ° C.

Yield: 76.6% of theory.

Example I

3-methoxy-anthranilic acid methyl ester.

133 g (0.63 mol) of 3-methoxy-2-nitrobenzoic acid methyl ester was dissolved in 1000 ml of toluene and hydrogenated in an autoclave at room temperature and 5 bar hydrogen pressure in the presence of platinum over 2 hours. The catalyst was filtered off, the mixture dried with sodium sulfate and the toluene distilled off in vacuo.

Oil, RF value 0.8 (silica gel plate: chloroform / acetone = 9: 1).

Yield: 110 g (96.4% of theory).

Because of its relative instability, it is not appropriate to store the substance, but immediately analogous to Example A to react further.

Example J

6-methoxy-anthranilic acid methyl ester hydrochloride.

A) 2-Cyano-3-methoxy-aniline.

110 g (0.617 mol) of 2-methoxy-6-nitro-benzonitrile was dissolved in 1 liter of methanol and hydrogenated in the presence of 10% of palladium carbon at room temperature and 5 bar hydrogen pressure within 1 hour in an autoclave. The catalyst was filtered off, the solvent was distilled off and the residue was recrystallized from ethanol / diisopropyl ether.

Mp: 142-143 ° C.

Yield: 54.8 g (59.9% of theory).

B) 6-Methoxy-anthranilic acid.

46

DK 164860 B

54 g (0.364 mol) of the product prepared by a) was heated together with 800 ml of 25% aqueous potassium hydroxide solution for 16 hours at reflux. After cooling, the reaction solution was brought to pH = 6 by the addition of acetic acid and extracted several times each with ½ liter of acetic acid ethyl ester. The combined extracts were dried over sodium sulfate and the acetic acid ethyl ester was distilled off. The residue was purified by column chromatography (silica gel, ethylene chloride / acetone = 19: 1). The total fractions were reduced to dryness.

Mp. 76-78 ° C.

Yield: 37.5 g (61.7% of theory).

c) 6-Methoxy-anthranilic acid methyl ester hydrochloride.

The acid obtained at b) (37.5 g = 0.22 mol) was dissolved in 500 ml of methanol and the solution was added for 2 hours on concentrated sulfuric acid dried hydrogen chloride. This precipitated a thick crystal porridge added to 500 ml of ether, suctioned off and finally washed once with 20 ether.

Mp: 209 ° C (dec.).

Yield: 36.5 g (75.2% of theory).

Example K

2 5 4-Methoxy-anthranilic acid methyl ester.

a) 3- (Isonitroso-acetamido) anisole.

1480 g (10.38 mole) of sodium sulfate and 225 g (1.36 mole) of chlorohydrate were dissolved in 6 liters of water and heated to 50 ° C. To this was added, with stirring, a solution of 30 154 g (1.25 moles) of m-anisidine in 750 ml of water and 125 ml of concentrated hydrochloric acid. Five minutes later, a solution of 275 g (3.96 mole) of hydroxylaramonium hydrochloride in 1.25 liters of water was added and heated to 95 ° C. With continued stirring, it was cooled to room temperature, the precipitate was sucked off, washed with water and dried. Mp: 165-166 ° C.

Yield: 242.5 g (99.9% of theory).

47 DK 164bbU b

Analogously, the following compounds were prepared: 4- (Isonitroso-acetamido) -3-methyl-anisole.

Mp: 166-167 ° C.

Yield: 94.1% of theory.

4- (Isonitroso-acetamido) -2-methyl-anisole.

Mp: 169-171 ° C.

Yield: 86.2% of theory.

2-Chloro-4- (isonitroso-acetamido) anisole.

Mp: 208 ° C.

Yield: 91.6% of theory, b) 6-Methoxy-isatin.

At 60 ° C, 140 g (0.72 mole) of 3- (isonitroso-acetamido) anisole was stirred into 720 g of polyphosphoric acid. The mixture was then heated to 100 ° C. At this temperature, it was stirred for a further 30 minutes, then the reaction mixture was cooled and poured under stirring to 4 20 liters of 30 ° C hot water. After standing overnight, the precipitate was suctioned off, washed with water and boiled with acetone / chloroform = 1: 1. The solution was dried over sodium sulfate and the solvent was distilled off. The residue was stirred with ethanol, suctioned off and dried at room temperature.

Mp: 237-238 ° C.

Yield: 84.2 g (65.9% of theory).

Analogously, the following compounds were prepared: 5-Methoxy-7-methyl-isatin.

Mp: 265-266 ° C.

Yield: 36% of theory.

5-methoxy-6-methyl isatin.

Mp: 254-256 ° C.

Yield: 87.2% of theory.

DK 164860B

48 6- Chloro-5-methoxy-isatin.

Mp: 247 ° C.

Yield: 33.2% of theory.

C) 4-Methoxy-anthranilic acid methyl ester.

158 g (0.89 mol) of 6-methoxy-isatin was suspended in 1300 ml of methanol and a solution of 54 g (1.34 mol) of sodium ethylate in 500 ml of methanol was added. To this, 108 ml (1.07 mole) of 30% hydirogen peroxide 10 was added with stirring and stirred for a further 30 minutes. The flask content was reduced to half the volume of water added and adjusted with glacial acetic acid to pH = 5-6. After extraction with methylene chloride, the mixture was suctioned on silica, dried over sodium sulfate, and the solvent was distilled off. The residue was recrystallized in petroleum ether / cyclohexane = 2: 1.

Mp: 80-82 ° C.

Yield: 109 g (67.7% of theory).

Analogously, the following compounds were prepared: 5-Methoxy-3-methyl-anthranilic acid methyl ester.

Mp: 81-82 ° C.

Yield: 59.6% of theory.

5-methoxy-4-methyl-anthranilic acid methyl ester.

Mp: 84-86 ° C.

Yield: 82.2% of theory.

Example L

8-Chloro-6-methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 7-chloro-6-methoxy-4,4-dimethyl-4H-3,1-benzoxazine-2 -on.

A solution of 79 g (0.38 mol) of 6-methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one in 1000 ml of chloroform was added 56.68 g (0.42 mol) of sulforyl chloride and stirred. 35 for 6 hours at 10-20 ° C. After standing overnight, the reaction mixture was added an aqueous sodium carbonate solution 49

DK 164860 B

solution, the organic phase was isolated, washed with water, dried over sodium sulfate and the chloroform was distilled off. The residue was partitioned column chromatographically into the isomers (silica gel, ethylene chloride / acetone = 19: 1). The 5 total fractions were reduced to dryness and the residue was recrystallized from acetic acid ethyl ester / diisopropyl ether.

1) 8-Chloro-6-methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Mp: 156-157 ° C

Yield: 47.3 g (51.6% of theory).

2) 7-Chloro-6-methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Mp: 165-167 ° C.

Yield: 18.9 g (20.6% of theory).

Example M

8-Bromo-6-methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 7-bromo-6-methoxy-4,4-dimethyl-4H-3,1-benzoxazine-2 -on.

82.7 g (0.4 mole) of 6-methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one was dissolved in 800 ml of dioxane and added dropwise 67.1 g (21.5) at room temperature. ml = 0.42 mol) of bromine. After 3 hours of stirring, an additional 67.1 g of bromine was added and after a further 3 hours a third of bromine 67.1 g of stirring was continued overnight. The reaction mixture was then added with ice water and sodium hydrogen sulfite solution and extracted with acetic acid ethyl ester. The extract was washed with water, dried over sodium sulfate and the acetic acid ethyl ester distilled off. The residue was column chromatographed into the isomers (silica gel, ethylene chloride / acetone = 60: 1). The pure fractions were reduced and recrystallized from acetic acid ethyl ester / diisopropyl ether.

50

DK 164860 B

1) 8-Bromo-6-methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Mp. 128-130 ° C (still contained slightly 7,8-dibromo-6-methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one).

Yield: 45 g (39.3% of theory).

2) 7-Bromo-6-methoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Mp: 174-175 ° C.

Yield: 33.7 g (29.5% of theory).

Example N

6-acetoxy-8-chloro-4H-3, l-benzoxazin-2-one.

14.5 g (0.07 mol) of 6-acetoxy-4H-3,1-benzoxazin-2-one (prepared from 6-hydroxy-4H-3,1-benzoxazin-2-one and acetanic anhydride. 173-175 ° C) was dissolved in 150 ml of glacial acetic acid, 10.8 g (6.5 ml = 0.08 mol) of sulforyl chloride was added and stirred for 36 hours at room temperature. After addition of 30 ml of ether, the mixture was cooled to 0 ° C, the precipitate was aspirated, washed with ether and dried.

Mp: 204-205 ° C.

Yield: 7.7 g (45.5% of theory).

Example O

8-Chloro-6-hydroxy-4H-3, l-benzoxazin-2-one.

7.6 g (31.4 mmol) of 6-acetoxy-8-chloro-4H-3,1-benzoxazin-2-one was suspended in 50 ml of methanol and 20 ml (40 mmol) of 2 n sodium hydroxide solution was added with stirring. The clear solution immediately obtained was stirred for an additional 10 minutes at room temperature, water was added and acidified with acetic acid. The precipitate was sucked off and recrystallized from isopropanol.

Mp: 250 ° C (dec.).

Yield: 3.3 g (52.7% of theory).

LMV IDH-OOU D

51

Manufacture of end products:

Example 1 6- [4- (4-Bromo-phenylmercapto) -butoxy] -4,4-dimethyl-4H-5,1-benzoxazin-2-one.

6.23 g (0.033 mol) of 4-bromothiophenol and 8.28 g (0.06 mol) of potassium carbonate were stirred in 100 ml of molecular sieve dried dimethyl sulfoxide under nitrogen atmosphere at room temperature for 15 minutes and then 8.51 g (0 (Mole) 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one. After stirring for 1 hour at room temperature, portion water was added until a thick crystal porridge was obtained. The mixture was suction dried, dried and unicrystallized in acetic acid ethyl ester / diisopropyl ether.

Mp: 151-152 ° C.

Yield: 9.2 g (70.3% of theory).

Example 2 6- [4- (4-Bromo-3-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

9.2 g (0.02 mol) of 6- [4- (4-bromo-3-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one Dissolve in 100 ml glacial acetic acid and add 2 ml (0.02 mol) 30% hydrogen peroxide. The mixture was stirred for 3 hours at room temperature, poured into 400 ml of water and extracted 3 times with acetic acid ethyl ester. The organic phase was washed with water, dried over sodium sulfate and the acetic acid ethyl ester was distilled off. The first residue was recrystallized from acetic acid ethyl ester / di-isopropyl ether.

Mp: 133-134 ° C.

Yield: 8.1 g (85.2% of theory).

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Example 3 4,4-Dimethyl-6- [4- (2-pyridylsulfonyl) -butoxy] -4H-3,1-benzoxazin-2-one.

3.58 g (0.01 mole) of 4,4-dimethyl-6- [4- (2-pyridyl-5-mercapto) -butoxy] -4H-3,7-benzoxazin-2-one was dissolved in 60 ml of formic acid and added 2 5 ml (0.025 mol) of 30% hydrogen peroxide. After stirring for 3 hours at room temperature, portions were diluted with water, extracted with acetic acid ethyl ester, the organic phase was dried over sodium sulfate and the acetic acid ethyl ester was distilled off. For purification, the mixture was chromatographed on a silica gel column (0.05 to 0.2 mm particle size) with a chloroform / ethanol (40: 1) mixture and the combined fractions were recrystallized after distilling off the elution mixture in acetic acid ethyl ester.

Mp. 142-143 ° C.

Yield; 2.1 g (53.8% of theory).

Example 4 6- [4- (3,4-Dichloro-phenylsulfinyl) butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

A solution of 1.9 g (0.01 mole) of 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4.1 g (0.0125 mole) of 4- (3, 4-Dichloro-phenyl-sulfinyl) -butyl bromide (m.p. 25 63-64 ° C) in 40 ml of dimethyl sulfoxide was added 3.5 g (0.025 mol) of potassium carbonate and stirred for 3 hours at 40 ° C. After cooling, ample ice water was added and extracted with chloroform. The extract was washed with water, dried over sodium sulfate and the chloroform distilled off. The residue was recrystallized from isopropanol / diisopropyl ether.

Mp: 138 ° C.

Yield: 1.9 g (43% of theory).

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DK 164860 B

Example 5 6- (4-Phenylmercapto-butoxy) -4H-3,1-benzoxazin-2-one.

To an ethanolic sodium ethylate solution prepared from 150 ml of ethanol and 0.92 g (9.04 mol) of sodium was added 4.95 g (0.03 mol) of 6-hydroxy-4H-3,1-benzene. oxazin-2-one and the mixture was heated to reflux. The hot mixture was added 10 g (0.04 mole) of 4-phenylmercapto-butyl bromide prepared from thio-phenol and excess 1,4-dibrorabutane (Kpo, 03 mb = 10 95-104 ° C) and stored for an additional 2 hours to reflux. The cooled reaction solution was poured into ice water and extracted with acetic acid ethyl ester. The extract was washed with water, dried over sodium sulfate and the acetic acid ethyl ester distilled off in vacuo.

The residue was recrystallized from cyclohexane / acetic acid ethyl ester.

Mp: 96-97 ° C.

Yield: 51.7% of theory.

Example 6 6- [4- (3,4-Dichloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

A solution of 32.65 g (0.074 mol) of 6- [4- (3,4-dichloro-phenylsulfonyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one in 300 To dimethyl formamide, 66.6 g (0.35 mole) of p-toluenesulfonic acid monohydrate and 42.9 g (0.15 mole) of O-mesylene sulphonyl 1-acethydroxamic acid ethyl ester were added and stirred for 30 hours at room temperature. After adding ice water, the solution was extracted with acetic acid ethyl ester, the acetic acid ethyl ester phase washed with water, dried over sodium sulfate and the acetic acid ethyl ester distilled off in vacuo. The residue was dissolved in 200 ml of methanol and the solution was added with so much 2 n sodium hydroxide solution that it reacted alkaline. Upon addition of 35 water, the reaction product was precipitated, extracted with acetic acid ethyl ester, the extract washed with water and 54

DK 164860 B

dried over sodium sulfate. The residue remaining after distillation of the acetic acid ethyl ester was recrystallized in acetic acid ethyl ester / diisopropyl ether.

Mp: 166-167 ° C.

Yield: 28.3 g (83.8% of theory).

Example 7 6- [4- (2-Pyridylsulfonyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

3.58 g (0.01 mole) of 6- [4- (2-pyridylmercapto) butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one was dissolved in 100 ml of chloroform and 4.3 g (0.025 mole) of m-chloro-perbenzoic acid were added with stirring. After 2 hours of stirring, an additional 2 g of m-chloro-perbenzoic acid was added and the mixture was allowed to stand overnight. The chloroform phase is shaken with water, the organic phase is dried over sodium sulfate and the chloroform is distilled off. The uniform residue was purified column chromatographically (silica gel; grain size: 0.05 to 0.2 mm, chloroform s ethanol = 40: 1). The total 20 fractions were reduced and the residue was triturated with acetic acid ethyl ester / ether. The crystals thus obtained were sucked off and dried at 50 ° C.

Mp: 90-91 ° C.

Yield: 1.0 g (26.7% of theory).

25

Example 8 6 - [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

2.14 g (0.005 mole) of 6- [4- (3,4-dichloro-phenylmer-capto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one was dissolved in 50 ml methanol, a solution of 1.3 g (0.06 mole) of sodium metaperiodate in 10 ml of water was added and stirred for 2 hours at room temperature. Then, for a further 3 hours to reflux, the volume of the reaction mixture was reduced to ca. 3/4 and stirred with water. The separated oil was isolated by decanting 55

DK 164860 B

from the solvent and taken up in hot isopropanol / di-isopropyl ether. On cooling, crystals of m.p. 138-139 ° C were precipitated.

Yield; 1.6 g (72.4% of theory).

5

Example 9 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

To a solution of 3.2 g (0.0075 mol) of 6- [4-3,4-10 dichlorophenylmercapto) butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one in 50 ml methylene chloride was dropped at -70 ° C a solution of 1 g (0.0085 mole) of sulfuryl chloride in 5 ml of methylene chloride with stirring and after completion of the stirring was continued at -70 ° C for a further 15 hours. After warming to room temperature, aqueous soda solution was added with vigorous stirring, the organic phase was isolated from the aqueous, washed with water and dried over sodium sulfate. The residue remaining after distillation of the methylene chloride was recrystallized from isopropanol / diisopropyl ether.

Mp: 138-139 ° C.

Yield: 2.1 g (63.3% of theory).

Example 10 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

To a solution of 2.13 g (0.005 mol) of 6- [4- (3,4-dichloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one in 50 ml of methanol was added little by little under 1 g (0.0056 mol) of N-bromosuccinimide. After 24 hours reaction time, 500 ml of 80 ° C hot water was added and the precipitate was aspirated after 2 hours of stirring. By recrystallization in isopropanol / diisopropyl ether crystals of melting point 35 136-139 ° C were obtained.

Yield: 1.55 g (70.1% of theory).

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Example 11 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -1,4,4-trimethyl-4H-3,1-benzoxazin-2-one.

A solution of 1.1 g (0.0025 mol) of 6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 1 ml of methyl iodide in 30 ml of methylene chloride were added 30 ml of 2 n sodium hydroxide (0.06 mol) and a spatula tip tetrabutylammonium hydrogen sulfate and stirred for 18 hours at room temperature. The organic phase was isolated, washed twice with water, dried over sodium sulfate and the methylene chloride distilled off. The residue was purified by column chromatography (silica gel, chloroform / acetone = 40: 1). The combined fractions were reduced, the residue was stirred with diisopropyl ether, the crystal crop was sucked off and dried.

Mp 90-92 ° C.

Yield: 0.31 g (27.3% of theory).

Example 12 6- [4- (3,4-Dichloro-N-methanesulfonyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

2.3 g (0.005 mol) of 6- [4- (3,4-dichloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one was dissolved in 50 ml chloroform and 0.5 ml of pyridine was added.

To this solution was added 1.2 g (0.01 mole) of methanesulfonyl chloride and stirred for 20 hours at room temperature. The chloroform phase was washed several times with water, dried over sodium sulfate and the chloroform distilled off. The residue was purified by column chromatography (silica gel, chloroform / ethanol - 30: 1). The combined fractions were reduced and the residue was oxygen crystallized in butanol / dimethyl formamide.

Mp: 198-200 ° C.

Yield: 2.4 g (89.6% of theory).

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Example 13 6- [4- (3,4-Dimethoxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-5 chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethoxy-thiophenol.

Melting point: 140-142 ° C.

Yield: 65.9% of theory.

Example 14 6- [4- (4-Methoxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-methoxy-thiophenol.

Melting point: 92-94 ° C.

Yield: 55.5% of theory.

Example 15 6- [4- (4-Hydroxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-hydroxythiophenol.

Melting point: 152-154 ° C.

Yield: 92.8% of theory.

Example 16 6- [4- (4-Biphenylyl mercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 4-phenylthiophenol.

Melting point: 120-122 ° C.

Yield: 87.2% of theory.

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Example 17 6- [4- (3-Methoxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3-methoxy-thiophenol.

Melting point; 115-116 ° C.

Yield; 79.6% of theory.

Example 18 6- [4- (3-Methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3-methylthiophenol.

Melting point; 103-105 ° C.

Yield; 80.8% of theory.

Example 19 6- [4- (3,5-Di-tert.butyl-4-hydroxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,5-di-tert.butyl-4-hydroxythiophenol.

Melting point: 86-87 ° C.

Yield: 76.2% of theory.

Example 20 6- [4- (4-Amino-3,5-dibromo-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 4-amino-3,5-dibromo-thiophenol.

Melting point: 152-155 ° C.

Yield: 85.5% of theory.

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Example 21 6- (4-n-Octylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and n-octylmercaptan. Oil, RF value: 0.8 (silica gel plate; chloroform / acetone = 9: 1).

Yield: 96.1% of theory.

C22H35NO3S (393.59) Calculated: C 67.14 H 8.96 N 3.56 S 8.15

Found: 67.31 9.00 3.57 8.25

Example 22 6- (4-Cyclohexylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and cyclohexylmercaptan.

Melting point: 105-107 ° C.

Yield: 82.5% of theory.

Example 23 6- [4- (4-Methyl-phenylmercapto) -butoxy] -4,4-di-n-hexyl-4h-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one 25 and 4-methyl-thiophenol.

Melting point: 76-78 ° C.

Yield: 78.1% of theory.

Example 24 6- [4- (4-Cyclohexyl-phenylmercapto) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one (oil, RF: 0.7; silica gel plate; chloroform) ) acetone = 19: 1) and 4-cyclohexylthiophenol.

Melting point: 87-89 ° C.

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Yield: 75.4% of theory.

Example 25 6- [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and 3,4-dichloro-thiophenol.

Melting point: 63-64 ° C.

Yield: 67.9% of theory.

Example 26 6- [4- (4-Acetamido-phenylmercapto) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one 15 and 4-acetamido-thiophenol. Oil, RF value: 0.5 (silica gel plate: chloroform / ethanol = 9: 1).

Yield: 98.2% of theory.

Example 27 6- [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and 3,4-dichloro-thiophenol.

Melting point: 181-182 ° C.

Yield: 77% of theory.

Example 28 6- [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dichloro-thiophenol.

Melting point: 155-156 ° C.

Yield: 72.8% of theory.

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Example 29 6- [4- (4-Acetamido-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-acetamido-thiophenol.

Melting point: 158 ° C.

Yield: 56.3% of theory.

Example 30 6- [4- (2-Pyridylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 2-mercaptopyridine.

Melting point: 137-138 ° C.

Yield: 72.5% of theory.

Example 31 6- [4- (4-Cyclohexyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-cyclohexylthiophenol.

Melting point: 109-110 ° C.

Yield: 47% of theory.

Example 32 6- [4- (4-Methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 4-methylthiophenol.

Melting point: 120-121 ° C.

Yield: 69.1% of theory.

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Example 33 6- [4- (4-Bromo-3-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4 / 4-dimethyl-4H-3,1-benzoxazin-2-one and 4 ”bromo-3-methyl-thiophenol.

Melting point: 129-130 ° C.

Yield: 57.0% of theory.

Example 34 6- [4- (4-Fluoro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-fluoro-thiophenol.

Melting point: 125-126 ° C.

Yield: 75.5% of theory.

Example 35 6- [4- (4-tert-Butyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-tert-butyl-thiophenol.

Melting point: 119-120 ° C.

Yield: 76.6% of theory.

Example 36 6- (4-Benzylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and benzylmercaptan.

Melting point: 90-9 ° C.

Yield: 64.6% of theory.

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Example 37 6- (4-Methylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and methyl mercaptan.

Melting point: 98-99 ° C.

Yield: 75.4% of theory.

Example 38 6- [4- (4-Methyl-phenylmercapto) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and 4-methylthiophenol.

Melting point: 149-150 ° C.

Yield: 81.4% of theory.

Example 39 6- [4- (4-Methyl-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4H-3,1-benzoxazin-2-one and 4-methyl-thiophenol.

Melting point: 125-126 ° C.

Yield: 74.7% of theory.

Example 40 6- [4- (4-Cyclohexyl-phenylmercapto) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and 4-cyclohexylthiophenol.

Melting point: 173-175 ° C.

Yield: 82.3% of theory.

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Example 41 6- [4- (4-Cyclohexyl-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4H-3,1-benzoxazin-2-one and 4-cyclohexylthiophenol.

Melting point: 134-135 ° C.

Yield: 60.3% of theory.

Example 42 6- [4- (4-Acetamido-phenylmercapto) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and 4-acetamido-thiophenol. o 15 Melting point: 115 C (dec.).

Yield: 96.8% of theory.

Example 43 6- [4- (4-Acetamido-phenylmercapto) -butoxy] -4H-3,1-benz-oxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4H-3,1-benzoxazin-2-one and 4-acetamido-thiophenol.

Melting point: 163-164 ° C.

Yield: 71.6% of theory.

Example 44 6- [2- (3,4-Dichloro-phenylmercapto) -ethoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (2-chloroethoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 3,4-dichloro-thiophenol.

Melting point: 145-146 ° C.

Yield: 69.1% of theory.

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Example 45 6- [3- (3,4-Dichloro-phenylmercapto) -propoxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 5 6- (3-chloropropoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dichloro-thiophenol.

Melting point: 115-116 ° C.

Yield: 88.9% of theory.

Example 46 6- [3- (4-Cyclohexyl-phenylmercapto) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (3-chloropropoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-cyclohexylthiophenol.

Melting point: 113-114 ° C.

Yield: 58.1% of theory.

Example 47 6- [4- (3,4-Dimethyl-phenylmercapto) -butoxy] -4H-3,1-benz-oxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4H-3,1-benzoxazin-2-one and 3,4-dimethyl-thiophenol.

Melting point: 124-125 ° C.

Yield: 73% of theory.

Example 48 6- [5- (4-Cyclohexyl-phenylmercapto) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (5-bromopentoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 4-cyclohexylthiophenol.

Melting point: 108-110 ° C.

Yield: 62.6% of theory.

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Example 49 6- [5- (3,4-Dichloro-phenylmercapto) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 5 6- (5-bromopentoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dichloro-thiophenol.

Melting point: 110-112 ° C.

Yield: 81.3% of theory.

Example 50 6- [4- (4-tert-Butyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-tert-butyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 115 ° C.

Yield: 53.8% of theory.

Example 51 6- [4- (4-Acetamido-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-acetamido-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 180 ° C.

Yield: 55.9% of theory.

Example 52 6- (4-Phenylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- (4-phenylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benz-oxazin-2-one and hydrogen peroxide.

Melting point: 64-66 ° C.

Yield: 68.4% of theory.

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Example 53 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 5- [4- (3,4-dichloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 139-140 ° C.

Yield: 83.8% of theory.

Example 54 6- [4- (4-Chloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-chloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 135-136 ° C.

Yield: 66.3% of theory.

Example 55 6- [4- (4-Cyclohexyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-cyclohexyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 147-148 ° C.

Yield: 74.3% of theory.

Example 56 6- [4- (4-Methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 124-125 ° C.

Yield: 76.0% of theory.

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Example 57 6- [4- (4-Fluoro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one.

Prepared analogously to Example 2 from 5 6- [4- (4-fluoro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 118-120 ° C.

Yield: 79.2% of theory.

Example 58 6- [4- (3,4-Dimethoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (3,4-dimethoxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 157-158 ° C.

Yield: 82.6% of theory.

Example 59 6- [4- (4-Methoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-methoxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 130-133 ° C.

Yield: 82.9% of theory.

Example 60 6- [4- (4-Hydroxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-hydroxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 157-160 ° C.

Yield: 44.9% of theory.

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Example 61 6- [4- (4-Biphenylylsulfinyl) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one.

Prepared analogously to Example 2 from 5 6- [4- (4-biphenylyl mercapto) butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 155-157 ° C.

Yield: 68.0% of theory.

Example 62 6- [4- (3-Methoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (3-methoxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Oil, RF value: 0.55 (silica gel plate; chloroform / ethanol = 9: 1).

Yield: 88.4% of theory.

C21H25N05S (403.5)

Calculated: C 62.51 H 6.24 N 3.47 S 7.95 Found: 62.31 6.17 3.33 7.84

Example 63 6- [4- (3-Methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (3-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Oil, RF value: 0.3 (silica gel plate? Chloroform / adetone = 9: 1).

Yield: 87.1% of theory.

C 21 H 25 NO 4 S (387.5) Calculated: C 65.09 H 6.50 N 3.61 S 8.27

Found: 64.98 6.65 3.53 8.30

Example 64 6- [4- (4-Amino-3,5-dibromo-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

35 Prepared analogously to Example 2 from

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6- {4- (4-Amino-3,5-dibromophenylmercapto) butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 169-172 ° C.

Yield: 35.2% of theory.

Example 65 6- [4- (3,5-Di-tert-butyl-4-hydroxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (3,5-di-tert-butyl-4-hydroxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazine-2 on and hydrogen peroxide.

Melting point: 177-179 ° C.

Yield: 74.6% of theory.

Example 66 6- [4- (4-Bromo-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-bromo-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 137-138 ° C.

Yield: 79.8% of theory.

Example 67 6- [4- (4-Methyl-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-methyl-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 143-144 ° C.

Yield: 82.2% of theory.

Example 68 6- [4- (4-Cyclohexyl-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-cyclohexyl-phenylmercapto) -butoxy] -4H-3,1- 71

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benzoxazin-2-one and hydrogen peroxide.

Melting point: 118-119 ° C.

Yield: 81.5% of theory.

Example 69 5- [4- (4-Acetamido-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-acetamido-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 183-184 ° C.

Yield: 84.0% of theory.

Example 70 6- [4- (3,4-Dimethyl-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (3,4-dimethyl-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point; 119-120 ° C.

Yield: 57.0% of theory.

Example 71 6- (4-Phenylsulfinyl-butoxy) -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- (4-phenylmercapto-butoxy) -4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 115-116 ° C.

Yield: 66.7% of theory.

Example 72 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (3,4-dichloro-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 169-170 ° C.

Yield: 91.8% of theory.

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Example 73 6- [4- (4-Chloro-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 5 6- [4- (4-chloro-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 169-171 ° C.

Yield: 86.0% of theory.

Example 74 6- (4-Benzylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- (4-benzylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 122 ° C.

Yield: 71.0% of theory.

Example 75 6- (4-Methylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- (4-methylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 124-126 ° C.

Yield: 68.1% of theory.

Example 76 6- (4-Cyclohexylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- (4-cyclohexylmercapto-butoxy) -4,4-dimethyl-4H-3, Ι-ΙΟ benzoxazin-2-one and hydrogen peroxide.

Melting point: 115 ° C.

Yield: 76.9% of theory.

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Example 77 6- [4- (4-Acetamido-phenylsulfinyl) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 5 6- [4- (4-acetamido-phenylmercapto) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 206-207 ° C.

Yield: 53.5% of theory.

Example 78 6- [4- (4-Methyl-phenylsulfinyl) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 200-201 ° C.

Yield: 62.0% of theory.

Example 79 6- [4- (4-Cyclohexyl-phenylsulfinyl) -butoxy] -4,4-di-cyclohexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-cyclohexyl-phenylmercapto) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: from 146 ° C (dec.).

Yield: 89.3% of theory.

Example 80 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (3,4-dichloro-phenylmercapto) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 186-187 ° C.

Yield: 49.2% of theory.

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Example 81 6- [4- (4-Methyl-phenylsulfinyl) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 5 6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 78-79 ° C.

Yield: 87.3% of theory.

Example 82 6- [4- (4-Cyclohexyl-phenylsulfinyl) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-cyclohexyl-phenylmercapto) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 72-75 ° C.

Yield: 71.4% of theory.

. Example 83 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (3,4-dichloro-phenylmercapto) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 8 3-8 5 ° C.

Yield: 71.7% of theory.

Example 84 6- [4- (4-Acetamido-phenylsulfinyl) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-acetamido-phenylmercapto) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Oil, RF value: 0.48 (silica gel plate: chloroform / ethanol = 9: 1).

Yield: 43.8% of theory.

C32H46N2 ° 5S (570.79) Calculated: C 67.34 H 8.12 N 4.91 S 5.62 75

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Found: C 67.52 H 7.94 N 4.95 S 5.78

Example 85 6- [2- (3,4-Dichloro-phenylsulfinyl) -ethoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [2- (3,4-dichloro-phenylmercapto) -ethoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 200-201 ° C.

Yield: 63.3% of theory.

Example 86 6 - [3- (3,4-Dichloro-phenylsulfinyl) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [3- (3,4-dichloro-phenylmercapto) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 157-158 ° C.

Yield: 76.3% of theory.

Example 87 6- [3- (4-Cyclohexylphenylsulfinyl) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [3- (4-cyclohexyl-phenylmercapto) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Oil, RF value: 0.45 (silica gel plate: chloroform / ethanol = 25: 9).

Yield: 96.3% of theory.

C25H31NO4S (441.59)

Calculated: C 68.00 H 7.08 N 3.17 S 7.26

Found: 67.75 7.01 3.17 7.13 Example 88 6- [5- (4-Cyclohexyl-phenylsulfinyl) pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [5- (4-cyclohexyl-phenylmercapto) -pentoxy] -4,4-di-76

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methyl 4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Oil, RF value: 0.45 (silica gel plate: chloroform / ethanol = 9: 1).

Yield: 63.9% of theory.

C27H35NO4S (469.65)

Calculated: C 69.05 H 7.51 N 2.98 S 6.83

Found: 70.26 7.74 2.91 6.87

Example 89 6- [5- (3,4-Dichloro-phenylsulfinyl) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [5- (3,4-dichloro-phenylmercapto) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 119-120 ° C.

Yield: 83.8% of theory.

Example 90 6- [4- (3,4-Dimethoxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (3,4-dimethoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl acethydroxamsyre acid ethyl ester.

Melting point: 162-163 ° C.

Yield: 51.3% of theory.

Example 91 6- [4- (4-Methoxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-methoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetate-hydroxamic acid ethyl ester.

Melting point: 134-140 ° C.

Yield: 47.8% of theory.

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Example 92 6- [4- (4-Hydroxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 5- [4- (4-hydroxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetyl-hydroxamic acid ethyl ester.

Melting point: 182-184 ° C.

Yield: 28.4% of theory.

Example 93 6- [4- (3-Methoxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (3-methoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylensylphonyl-acetyl-hydroxamic acid ethyl ester.

Melting point: 102-105 ° C.

Yield: 31.9% of theory.

Example 94 6- [4- (4-Biphenylylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-biphenylylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid ethyl ester.

Melting point: 184-186 ° C.

Yield: 68.5% of theory.

Example 95 6- [4- (4-Amino-3,5-dibromo-phenylsulfoxymino) -butoxy] -30,4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-amino-3,5-dibromo-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfinyl -acethydroxamsyre acid ethyl ester.

Melting point: 206-208 ° C.

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Yield: 73.8% of theory.

Example 96 6- [4- (3,5-Di-tert-butyl-4-hydroxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (3,5-di-tert-butyl-4-hydroxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazine-2- one and 0-mesethylenesulfonylacetydroxamic acid ethyl ester.

Melting point: 176-178 ° C.

Yield: 65.8% of theory.

Example 97 6- [4- (3-Methyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (3-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethyroxamic acid. ethyl ester.

Melting point: 118-120 ° C.

Yield: 33% of theory.

Example 98 6- [4- (4-Fluoro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-fluoro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetyl-hydroxamic acid ethyl ester.

Melting point: 136-138 ° C.

Yield: 30.8% of theory.

Example 99 6- [4- (4-Bromo-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-bromo-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydroxam-79

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acid ethyl ester.

Melting point: 155-157 ° C.

Yield: 50% of theory.

Example 100 6- [4- (4- Bromo-3-methyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-bromo-3-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-10 acethydroxamsyre acid ethyl ester.

Melting point: 153-154 ° C.

Yield: 63.6% of theory.

Example 101 6- [4- (4-Cyclohexyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-cyclohexyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetyl-hydroxamic acid ethyl ester .

Melting point: 168-169 ° C.

Yield: 52.8% of theory.

Example 102 6- [4- (4-Methyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acet-hydroxamic acid. ethyl ester.

Melting point: 147-148 ° C.

Yield: 59.2% of theory.

Example 103 6- (4-Phenylsulfoxymino-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 80

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6- (4-Phenylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid ethyl ester.

Melting point: 152 ° C.

Yield: 71.7% of theory.

Example 104 6- [4- (4-Chloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 out. from 6- [4- (4-chloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetyl-hydroxamic acid ethyl ester.

Melting point: 132 ° C.

Yield: 61.6% of theory.

Example 105 6- [4- (4-tert-Butyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-tert-butyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl hydroxamic acid-acetic acid ethyl ester.

Melting point: 187 ° C.

Yield: 72% of theory.

Example 106 6- [4- (4-Acetamido-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acet-30 hydroxamic acid ethyl ester.

Melting point: 185 ° C.

Yield: 44% of theory.

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Example 107 6- [4- (4-Methyl-phenylsulfoxymino) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 5- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-di-n-hexyl-4H-3/1-benzoxazin-2-one and O-mesitylene sulfonyl hydroxamic acid-acetic acid ethyl ester.

Melting point: 89-91 ° C.

Yield: 87.5% of theory.

Example 108 6- [4- (4-Cyclohexyl-phenylsulfoxymino) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-cyclohexyl-phenylsulfinyl) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl acethydroxamsyre acid ethyl ester.

Melting point: 78-80 ° C.

Yield: 48.3% of theory.

Example 109 6- [4- (3,4-Dichloro-phenylsulfoxymino) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (3,4-dichloro-phenylsulfonyl) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl -25 acetyl hydroxamic acid ethyl ester.

Melting point: 106-108 ° C.

Yield: 66.9% of theory.

Example 110 6- [4- (4-Acetamido-phenylsulfoxymino) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and O-mesitylenesulfonyl-acetydroxamic acid ethyl ester.

Melting point: 146-148 ° C.

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Yield: 78% of theory.

Example 111 6- [4- (4-Acetamido-phenylsulfoxymino) -butoxy] -4,4-di-cyclohexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid. ethyl ester.

Melting point: 149-150 ° C.

Yield: 54% of theory.

Example 112 6- [4- (4-Methyl-phenylsulfoxymino) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid. ethyl ester.

Melting point: 176-177 ° C.

Yield; 58.6% of theory.

Example 113 6- [4- (4-Cyclohexyl-phenylsulfoxymino) -butoxy] -4,4-di-cyclohexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-cyclohexyl-phenylsulfinyl) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetre hydroxamic acid ethyl ester.

Melting point: 219-220 ° C.

Yield: 73.2% of theory.

Example 114 6- [4- (4-Methyl-phenylsulfoxymino) -butoxy] -4H-3,1-benz-oxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetydraxamic acid ethyl ester.

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Melting point: 153-154 ° C.

Yield: 60% of theory.

Example 115 6- [4- (4-Cyclohexyl-phenylsulfoxymino) -butoxy] -4H-3,1-5-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-cyclohexyl-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one and O-mesitylene-sulfonyl-acethydroxamic acid ethyl ester.

Melting point: 187-188 ° C.

Yield: 65% of theory.

Example 116 6- [4- (4-Acetamido-phenylsulfoxymino) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4H-3,1-benz-oxazin-2-one and O-mesitylene sulfonyl-acetyl-hydroxamic acid ethyl ester.

Melting point: 135-137 ° C.

Yield: 64.7% of theory.

Example 117 6- [5- (3,4-Dichloro-phenylsulfoxymino) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [5- (3,4-dichloro-phenylsulfinyl) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl acethydroxamic acid ethyl ester.

island

Melting point: 169-170 ° C

Yield: 85.7% of theory.

Example 118 6- [5- (4-Cyclohexyl-phenylsulfoxymino) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [5- (4-cyclohexyl-phenylsulfinyl) -pentoxy] -4,4-dimethyl-84

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thyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl acetate hydroxamic acid ethyl ester.

Melting point: 110-111 ° C.

Yield: 67.1% of theory.

Example 119 6- [3- (3,4-Dichloro-phenylsulfoxymino) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [3- (3,4-dichloro-phenylsulfinyl) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl hydroxamic acid-acetic acid ethyl ester.

Melting point: 135-136 ° C.

Yield: 67.8% of theory.

Example 120 6- [3- (4-Cyclohexyl-phenylsulfoxymino) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [3- (4-cyclohexyl-phenylsulfinyl) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acet-2 0 hydroxamic acid ethyl ester.

Melting point: 175-176 ° C.

Yield: 50.3% of theory.

Example 121 6- [2- (3,4-Dichloro-phenylsulfoxymino) -ethoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [2- (3,4-dichloro-phenylsulfinyl) -ethoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetyl hydroxamic acid ethyl ester.

Melting point: 139-140 ° C.

Yield: 64% of theory.

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Example 122 6- (4-Cyclohexylsulfoxymino-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 5 6- (4-cyclohexylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetydroxamic acid ethyl ester.

Melting point: 108-110 ° C.

Yield: 28% of theory.

Example 123 6- (4-Benzylsulfoxymino-butoxy) -4,4-dimethyl-4H-3,1-benz-oxazin-2-one.

Prepared analogously to Example 6 from 6- (4-benzylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benz-oxazin-2-one and O-mesitylenesulfonyl-acethydroxamic acid ethyl ester.

Melting point: 132-138 ° C.

Yield: 75% of theory.

Example 124 6- (4-n-Octylsulfoxymino-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- (4-n-octylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benz-oxazin-2-one and O-mesitylenesulfonyl-acethydroxamic acid ethyl ester.

Melting point: 82 ° C.

Yield: 73.2% of theory.

Example 125 6- [4- (4-Chloro-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 5 from 6-hydroxy-4H-3,1-benzoxazin-2-one and 4- (4-chloro-phenyl-mercapto) -butyl chloride (prepared from 4- (4-chloro-phenyl-mercapto) - butanol and thionyl chloride.

Oil, RF value: 0.25 (silica gel: petroleum ether / cyclohexane = 1: 1).

Melting point: 143-144 ° C.

Yield: 28% of theory.

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Example 126 6- [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 5 from 6-hydroxy-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-phenylmercapto) -butyl bromide (prepared from 10 3,4-dichloro-thiophenol and 1.4 -dibromo-butane, Kp

Melting point: 128-129 ° C.

Yield: 57% of theory.

Example 127 6- (4-Phenylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 5 from 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-phenylmercapto-butyl bromide (Kp g 03 mb: 95-104 ° C) · 20 Melting point: 108-109 ° C.

Yield: 52.5% of theory.

Example 128 6- [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 5 from 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-phenylmercapto) -butyl bromide.

Melting point: 155-156 ° C.

Yield: 53% of theory.

Example 129 6- [4- (4-Chloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 5 from 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (4-chloro-phenylmercapto) -butyl chloride.

Melting point: 150-151 ° C.

Yield: 55.6% of theory.

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Example 130 6- [4- (3,4-Dimethyl-phenylsulfoximino) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (3,4-dimethyl-phenylsulfinyl) -butoxy] -4H-3,1-benz-oxazin-2-one and O-mesitylene-sulfonyl-acetyl-hydroxamic acid-ethyl ester.

Melting point: 169-170 ° C.

Yield: 82.5% of theory.

Example 131 6- (4- (3,4-Dimethyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (3,4-dimethyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetroxamic acid ethyl ester.

Melting point: 162-163 ° C.

Yield: 70.4% of theory.

Example 132 6- [4- (3,4-Dimethyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethylthiophenol.

Melting point: 122-123 ° C.

Yield: 75.3% of theory.

Example 133 6- [6- (3,4-Dichloro-phenylmercapto) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (6-bromohexyloxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dichloro-thiophenol.

Melting point: 102-103 ° C.

Yield: 77.4% of theory.

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Example 134 6- [6- (3,4-Dimethoxy-phenylmercapto) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (6-bromohexyloxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethoxy-thiophenol.

Melting point: 153-154 ° C.

Yield: 89.4% of theory.

Example 135 6- (4-Phenylsulfonyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-phenylsulfonyl-butyl bromide (m.p. 57-58 ° C). Melting point: 155-156 ° C.

Yield: 53.7% of theory.

Example 136 6- [6- (3,4-Dichloro-phenylsulfoxymino) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [6- (3,4-dichloro-phenylsulfonyl) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl hydroxamic acid-acetic acid ethyl ester.

Melting point: 135-136 ° C.

Yield: 84.5% of theory.

Example 137 6 - [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-phenylmercapto) -butyl bromide (Kp g : 89

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153-160 ° C).

Melting point: 152-153 ° C.

Yield: 63.4% of theory.

Example 138 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4-ethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 4-ethyl-6-hydroxy-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-phenylsulfinyl) -butyl bromide.

Melting point: 83-84 ° C.

Yield: 61.9% of theory.

Example 139 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4-isopropyl-4H-3,1-benzoxazin-2-one Prepared analogously to Example 4 from 6-hydroxy-4-one isoproyl-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-phenylsulfinyl) -butyl bromide.

Melting point: 73-75 ° C.

Yield: 48.2% of theory.

Example 140 6- [4- (3,4-Dichloro-phenylsulfoximino) -butoxy] -4-ethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4-ethyl-4H-3,3-1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid ethyl ester.

Melting point: 132-133 ° C.

Yield: 60% of theory.

Example 141 6- [4- (3,4-Dichloro-N-p-toluehsulfonyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 12 from 6- [4- (3,4-dichloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and p-toluenesulfonic acid chloro-90

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chloride.

Melting point: 174-175 ° C.

Yield: 78.4% of theory.

Example 142 6- [4- (3,4-Dichloro-N-benzoyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 12 from 6- [4- (3,4-dichloro-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and benzoyl chloride.

Melting point: 189-190 ° C.

Yield: 67.6% of theory.

Example 143 6- [4- (3,4-Dimethoxy-N-acetyl-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

To a solution of 1 g (0.0022 mol) of 6- [4- (3,4-dimethoxy-phenyl sulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one In ml0 ml glacial acetic acid was added 1.5 ml of acetanhydride and stirred for 3 hours at room temperature. After the addition of ice water, 20 was extracted with chloroform, the chloroform or ash was washed with water and dried over sodium sulfate, then the chloroform was distilled off and recrystallized from acetic acid ethyl ester.

Melting point: 155-157 ° C.

Yield: 0.95 g (88% of theory).

Example 144 6- [4- (4-Phenyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (4-phenyl-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 106-108 ° C.

Yield: 94.7% of theory.

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Example 145 6- [4- (3, 5-Di-tert-butyl 4-hydroxy-N-acetyl-phenyl-sulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one . Prepared analogously to Example 143 from 5- [4- (3,5-di-tert-butyl-4-hydroxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazine-2 on and acet anhydride.

Melting point: 206-207 ° C.

Yield: 93.1% of theory.

Example 146 6- [4- (4-Amino-3,5-dibromo-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (4-amino-3,5-dibromo-phenylsulfoxymino) -butoxy] -15 4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride. Melting point: 198-200 ° C.

Yield: 86.2% of theory.

Example 147 6- [4- (4-tert-Butyl-N-acetyl-phenylsulfoxymino) -butoxy] -20 4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (4-tert-butyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 235-237 ° C.

Yield: 92.9% of theory.

Example 148 6- [4- (4-Methyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (4-methyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 109-110 ° C.

Yield: 83.6% of theory.

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Example 149 6- [4- (4-Bromo-3-methyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 5 6- [4- (4-bromo-3-methyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 152-154 ° C.

Yield: 85.5% of theory.

Example 150 6- [4- (3,4-Dichloro-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (3,4-dichloro-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 156-158 ° C.

Yield: 91.3% of theory.

Example 151 6- [4- (N-Acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- (4-phenylsulfoxymino-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 112-114 ° C.

Yield: 89.2% of theory.

Example 152 6- [4- (4-Chloro-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (4-chloro-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 120-122 ° C.

Yield: 86.9% of theory.

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Example 153 6- [4- (4-Methyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-di-hexhexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 5 6- [4- (4-methyl-phenylsulfoximino) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Oil, RF value: 0.4 (silica gel plate: chloroform / acetone = 9: 1).

Yield: 98.9% of theory.

C33H48N205S (584.82)

Calculated: C 67.78 H 8.27 S 5.48

Found: 67.89 8.31 5.60

Example 154 6- [4- (4-Cyclohexyl-N-acetyl-phenylsulfoxymino) -butoxy] -15,4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (4-cyclohexyl-phenylsulfoxymino) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 134-136 ° C.

Yield: 81.9% of theory.

Example 155 6- [4- (3,4-Dichloro-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (3,4-dichloro-phenylsulfoxymino) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Oil, RF value: 0.54 (silica gel plate: chloroform / acetone = 9: 1).

Yield: 68.8% of theory.

C32H44C12N2 ° 5S (639.70)

Calculated: C 60.08 H 6.93 Cl 11.08 s 5.01

Found: 59.87 7.13 11.20 4.95

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Example 156 6- [4- (4-Acetamido-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 5 6- [4- (4-acetamido-phenylsulfoxymino) -butoxy] -4,4-di-n-hexyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 122-124 ° C.

Yield: 83.6% of theory.

Example 157 6- [4- (4-Acetamido-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 43 from 6- [4- (4-acetamido-phenylsulfoximino) -butoxy] -4,4-di-cyclohecyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 146 ° C (dec.).

Yield: 78.3% of theory.

Example 158 6- [4- (4-Methyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (4-methyl-phenylsulfoximino) -butoxy] -4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 148-149 ° C.

Yield: 78.9% of theory.

Example 159 6- [4- (4-Acetamido-N-acetyl-phenylsulfoxymino) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (4-acetamido-phenylsulfoximino) -butoxy] -4H-3,1 -30-benzoxazin-2-one and acetanhydride.

Melting point: 200-201 ° C.

Yield: 73.7% of theory.

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Example 160 6- [4- (4-Methyl-N-acetyl-phenylsulfoxymino) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 5 6- [4- (4-methyl-phenylsulfoximino) -butoxy] -4H-3,1-benz-oxazin-2-one and acetanhydride.

Oil, RF value: 0.62 (silica gel plate: chloroform / acetic acid ethyl ester = 9: 1).

Yield: 45% of theory.

Example 161 6- [4- (4-Cyclohexyl-N-acetyl-phenylsulfoxymino) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (4-cyclohexyl-phenylsulfoximino) -butoxy] -4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 124-125 ° C.

Yield: 86.8% of theory.

Example 162 6- [4- (4-Cyclohexyl-N-acetyl-phenylsulfoxymino) -butoxy] -20 4,4-dicyclohexyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (4-cyclohexyl-phenylsulfoximino) -butoxy] -4,4-di-cyclohexyl-4H-3,1-benzoxazin-2-one and acetanhydride. Melting point: 130 ° C.

Yield: 70.2% of theory.

Example 163 6- [5- (3,4-Dichloro-N-acetyl-phenylsulfoxymino) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [5- (3,4-dichloro-phenylsulfoxymino) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 126-128 ° C.

Yield: 50.6% of theory.

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Example 164 6-15-- (4-Cyclohexyl-N-acetyl-phenylsulfoxymino) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 5- [5- (4-cyclohexyl-phenylsulfoxymino) -pentoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 95-96 ° C.

Yield: 83.5% of theory.

Example 165 6- [3- (4-Cyclohexyl-N-acetyl-phenylsulfoxymino) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [3- (4-cyclohexyl-phenylsulfoxymino) -propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 114-115 ° C.

Yield: 94.2% of theory.

Example 166 6- [3- (3,4-Dichloro-N-acetyl-phenylsulfoxymino) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [3- (3,4-dichloro-phenylsulfoxymino) propoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 198-200 ° C.

Yield: 81.2% of theory.

Example 167 6- [2- (3,4-Dichloro-N-acetyl-phenylsulfoxymino) -ethoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [2- (3,4-dichloro-phenylsulfoxymino) -ethoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 154-155 ° C.

Yield: 81.2% of theory.

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Example 168 6- [4- (3,4-Dimethyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 5- [4- (3,4-dimethyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 131-132 ° C.

Yield: 83.3% of theory.

Example 169 6- [6- (3,4-Dichloro-phenylsulfinyl) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [6- (3,4-dichloro-phenylmercapto) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 156-158 ° C.

Yield: 71.5% of theory.

Example 170 6- [6- (3,4-Dimethoxy-phenylsulfonyl) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [6- (3,4-dimethoxy-phenylmercapto) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 131-132 ° C.

Yield: 61.0% of theory.

Example 171 6- [4- (3,4-Dimethyl-N-acetyl-phenylsulfoxymino) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (3,4-dimethyl-phenylsulfoximino) -butox] -4H-3, Ι-ΙΟ benzoxazin-2-one and acetanhydride.

Resin, RF value: 0.7 (silica gel plate: chloroform / ethanol = 9: 1).

Yield 90.2% of theory.

C22H26N2 ° 5S (430.53) Calculated: C 61.38 H 6.09 N 6.51 S 7.45 98

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Found: C 61.79 H 6.32 N 6.24 S 7.38

Example 172 6 - [- (3,4-Dimethyl-N-acetyl-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (3,4-dimethyl-phenylsulfoxymino) -butoxy) -4,4-dimethyl-4H-3,1-benzoxazine-2-one acetate anhydride.

Melting point: 14 6 ° C.

Yield: 86.5% of theory.

Example 173 6- [6- (3,4-Dimethoxy-phenylsulfoxymino) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [6- (3,4-dimethoxy-phenylsulfinyl) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one ethyl ester.

Melting point: 108-109 ° C.

Yield: 83.9% of theory.

Example 174 6- [3- (3,4-Dichloro-phenylmercapto) propoxy] -4,4-isopropyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (3-chloropropoxy) -4-isopropyl-4H-3,1-benzoxazin-2-one and 3,4-dichloro-thiophenol.

Melting point: 109-111 ° C.

Yield: 75.7% of theory.

Example 175 4-Isopropyl-6- [3- (3,4-dimethoxy-phenylmercapto) -propoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (3-chloropropoxy) -4-isopropyl-4H-3,1-benzoxazin-2-one and 3,4-dimethoxy-thiophenol.

Melting point: 102-103 ° C.

Yield: 84.2% of theory.

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Example 176 6- [4- (3,4-Dichloro-N-acetyl-phenylsulfoxymino) -butoxy] -4-ethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 5 6- [4- (3,4-dichloro-phenylsulfoxymino) -butoxy] -4-ethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 156-158 ° C.

Yield: 87.31 of theory.

Example 177 6- [3- (3,4-Dichloro-phenylsulfinyl) propoxy] -4-isopropyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [3- (3,4-dichloro-phenylmercapto) propoxy] -4-isopropyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 58-60 ° C.

Yield: 83.3% of theory.

Example 178 6- [3- (3,4-Dimethoxy-phenylsulfinyl) -propoxy] -4-iso-propyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [3- (3,4-dimethoxy-phenylmercapto) -propoxy] -4-iso-propyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 5-8 ° C.

Yield: 91.1% of theory.

Example 179 6- [6- (3,4-Dichloro-N-acetyl-phenylsulfoxymino) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 43 from 6- [6- (3,4-dichloro-phenylsulfoximino) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Oil, RF value: 0.64 (silica gel plate: chloroform / ethanol = 9: 1).

Yield: 83.1% of theory.

C24H28C12H2 ° 5S (527'48> 35 Calc'd: C 54.65 H 5.35 S 6.08

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100

Found: C 54.30 H 5.34 S 6.06

Example 180 6- [4- (3,4-Dichloro-phenylsulfoxymino) -butoxy] -4-isopropyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4-isopropyl-4H-3,1-benzoxazin-2-one and O ethyl ester.

Melting point: 123-125 ° C.

Yield: 47.7% of theory.

Example 181 6- [6- (3,4-Dimethoxy-N-acetyl-phenylsulfoxymino) -hexyl-oxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [6- (3,4-dimethoxy-phenylsulfoxymino) -hexyloxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Oil, RF value: 0.65 (silica gel plate: chloroform / ethanol = 9: 1).

Yield: 83.5% of theory.

C26H34N2O7S (518.63)

C, 60.21; H, 6.61; S, 6.18

Found: 59.90 6.59 6.13

Example 182 6- [4- (3,4-Dichloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

3.3 g (0.0075 mol) of 6- [4- (3,4-dichloro-phenylsulfonyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one was stirred at 45 °. C in 50 ml polyphosphoric acid. After practically everything dissolved, 0.65 g (0.01 mole) of sodium azide was added in small portions within 30 minutes. Weak nitrogen gas evolution was noted.

The beige creamy foamy mass was stirred for 3 hours at 45-50 ° C and 150 g of ice was added. The resulting cloudy solution was adjusted to pH 8 with concentrated ammonia and the resinous product extracted

LI IV I DH-ODU D

101 with chloroform. The oily residue was recrystallized from acetic acid ethyl ester / diisopropyl ether.

White crystals were obtained.

Melting point: 166-167 ° C.

Yield: 2.0 g (58.6% of theory).

Example 183 6- [4- (3,4-Dichloro-phenylsulfinamino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4-10 (3,4-dichloro-phenylmercapto) butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O acid ethyl ester.

Melting point: 165-166 ° C.

Yield: 10% of theory.

Example 184 6- [3- (3,4-Dimethoxy-phenylsulfoxymino) -propoxy] -4-iso-propyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [3- (3,4-dimethoxy-phenylsulfinyl) -propoxy] -4-isopropyl-4H-20,1-benzoxazin-2-one ethyl ester.

Melting point: 123-125 ° C.

Yield: 77.3% of theory.

Example 185 6- [4- (3,4-Dichloro-N-p-toluenesulfonyl-phenylsulfimino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

4.26 g (0.01 mole) of 6- [4- (3,4-dichloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one were suspended in 50 ml of methanol. and added so much chloroform that a clear solution (about 80 ml) was obtained. To this was added a solution of 3.38 g (0.012 mol) of N-chloro-p-toluenesulfonic acid sodium salt in 30 ml of methanol and the mixture was allowed to stand for 4 hours at room temperature. To the yellow reaction solution was added ca.

35 ml of glacial acetic acid and the solvent were distilled off 102

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in a rotary evaporator (bath temperature: <20 ° C). The light brown cool residue was purified on a silica gel column (eluent: acetic acid ethyl ester / cyclohexane 4: 1). The combined fractions were reduced in a rotary evaporator 5 to dryness and the residue was recrystallized once in acetic acid ethyl ester / isopropanol.

Melting point: 162-163 ° C.

Yield: 2.0 g (33.6% of theory).

Example 186 6- [4- (3,4-Dichloro-N-p-toluenesulfonyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

0.6 g (0.001 mol) of 6- [4- (3,4-dichloro-Nβ-toluene-sulfonyl-phenylsulfimino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one was suspended. in 10 ml of methanol, 1 ml of 2N sodium hydroxide solution and 0.2 ml (0.002 mol) of 30% hydrogen peroxide were added and refluxed for 8 hours. Thereby a clear solution appeared which, after completion of the reaction, was reduced to dryness. The residue was purified on a silica gel column (chloroform). The total fractions 20 were reduced and recrystallized once in ethanol. Melting point: 174-175 ° C.

Yield: 0.27 g (44.1% of theory).

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Example 187 6- [3- (3,4-Dichloro-phenylsulfoximino) propoxy] -4-iso-propyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 5 6- [3- (3,4-dichloro-phenylsulfinyl) propoxy] -4-isopropyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl acetate hydroxamic acid ethyl ester.

Resin, RF value: 0.45 (silica gel plate: chloroform / ethanol = 19: 1).

Yield: 43.7% of tertiary ethics.

C20H22C12N2 ° 2S (457.38)

Calculated: C 52.52 H 4.85 S 7.01

Found: 52.49 5.12 6.63

Example 188 6- [3- (3,4-Dimethoxy-N-acetyl-phenylsulfoxymino) propoxy] -4-isopropyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [3- (3,4-dimethoxy-phenylsulfoxymino) -propoxy] -4-iso-propyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 73-75 ° C.

Yield: 81.4% of theory.

Example 189 6- [4- (4-Cyclohexyl-phenylmercapto) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-cyclobutoxy) -4,4-diethyl-4H-3,1-benzoxazin-2-one and 4-cyclohexyl-thiophenol.

Melting point: 85-88 ° C.

Yield: 69.1% of theory.

Example 190 6- [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-diethyl-4H-3,1-benzoxazin-2-one 35 and 3,4-dichloro-thiophenol.

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Melting point: 143-145 ° C.

Yield: 58.7% of theory.

Example 191 6- (4-Phenylmercapto-butoxy) -4,4-diethyl-4H-3,1-benz-5-oxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-diethyl-4H-3,1-benzoxazin-2-one and thiophenol.

Melting point: 104-106 ° C.

Yield: 69.8% of theory.

Example 192 6- [4- (3,4-Dimethyl-phenylmercapto) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-diethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethylthiophenol.

Melting point: 124-125 ° C.

Yield: 83.4% of theory.

Example 193 6- [4- (3,4-Dimethoxy-phenylmercapto) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-diethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethoxy-thiophenol.

Melting point: 110-111 ° C.

Yield: 72.6% of theory.

Example 194 6- [4- (4-Acetamido-phenylmercapto) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-diethyl-4H-3,1-benzoxazin-2-one and 4-acetamido-thiophenol.

Melting point: 90-9 2 ° C.

Yield: 62.9% of theory.

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Example 195 6- [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4-methyl-4H-3.1-benzoxazin-2-one.

Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4-methyl-4H-3,1-benzoxazin-2-one and 3,4-dichloro-thiophenol.

Melting point: 117-119 ° C.

Yield: 50.5% of theory.

Example 196 6- [4- (4-Methyl-phenylmercapto) -butoxy] -4-methyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4-methyl-4H-3,1-benzoxazin-2-one and 4-methylthiophenol.

Melting point: 111-113 ° C.

Yield: 54.4% of theory.

Example 197 6- [4- (4-Acetamido-phenylmercapto) -butoxy] -4-methyl-4H-3.1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4-methyl-4H-3,1-benzoxazin-2-one and 4-acetamido-thiophenol.

Melting point: 122-124 ° C.

Yield: 44.2% of theory.

Example 198 6- [4- (2-Benzthiazolylmercapto) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one.

Prepared analogously to Example lye from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 2-mercapto-benzthiazole.

Melting point: 183-184

Yield: 56.3% of theory.

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Example 199 6- [4- (4,6-Dimethyl-2-pyrimidinylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4,6-dimethyl-2-mercaptopyrimidine.

Melting point: 125-127 ° C.

Yield: 65.9% of theory.

Example 200 6- [4- (1-Oxido-2-pyridylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 2-mercapto-pyridine-1-oxide.

Melting point: 154-156 ° C.

Yield: 14.6% of theory.

Example 201 6- [4- (1,2,4-Triazol-3-yl-mercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3-mercapto-1,2,4-triazole.

Melting point: 181-183 ° C.

Yield: 42.2% of theoretical Example 202 6- [4- (2-Pyrimidinylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 2-mercapto-pyrimidine.

Melting point: 142-144 ° C.

Yield: 53.9% of theory.

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Example 203 6- [4- (4-Pyridylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-mercapto-pyridine.

Melting point: 153-155 ° C.

Yield: 64.2% of theory.

Example 204 8- [4- (4-Cyclohexyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H.3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 8- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-cyclohexylthiophenol.

Melting point: 109-110 ° C

Yield: 70.5% of theory.

Example 205 8- [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 8- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dichloro-thiophenol.

Melting point: 137-138 ° C.

Yield: 74.5% of theory.

Example 206 8- (4-Phenylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 8- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and thiophenol.

Melting point: 98-100 ° C.

Yield: 87.9% of theory.

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Example 207 8- [4- (3,4-Dimethyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 5 8- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethylthiophenol.

Melting point: 137-139 ° C.

Yield: 90.7% of theory.

Example 208 8- [4- (3,4-Dimethoxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 8- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethoxy-thiophenol.

Melting point: 116-117 ° C.

Yield: 93.8% of theory.

Example 209 8- [4- (4-Acetamido-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 8- (4-chlorobutoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-acetamido-thiophenol.

Melting point: 166-167 ° C Yield: 63.6% of theory.

Example 210 6- [4- (3,4-Dimethylphenylimercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

9.1 g (0.0234 mole) of 6- (4-methanesulfonyloxy-butoxy) -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3.5 g (0.025 mole) ) 3,4-Dimethyl-thiophenol is dissolved in 80 ml of dimethylformamide. With stirring, 6.9 g (0.05 mole) of potassium carbonate and finally 4 ml of water are added. The reaction mixture becomes briefly warm and after the heat mixture has died, it is stirred for another 2 hours at room temperature. After the addition of 109

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ice water is extracted with chloroform, the organic phase is washed with water, dried with sodium sulfate and the solvent is distilled off in vacuo. The residue is purified over a silica gel column (eluent: chloroform / ethanol = 40: 1).

Oil, RF value: 0.4 (silica gel plate: chloroform / ethanol = 9: 1).

Yield: 7.6 g (75.4% of theory).

C22H26N2 ° 5S (430.52) Calculated: C 61.38 H 6.09 N 6.51 S 7.45

Found: 61.10 6.07 6.24 7.28

Example 211 6- [4- (4-Acetamido-phenylmercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 210 from 6- (4-methanesulfonyloxy-butoxy) -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-acetamido-thiophenol.

Melting point: 203-205 ° C.

Yield: 69.2% of theory.

Example 212 6- [4- (4-Chloro-phenylmercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 210 from 6- (4-methanesulfonyloxy-butoxy) -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-chloro-thiophenol.

Melting point: 155-156 ° C.

Yield: 69.5% of theory.

Example 213 6- [4- (2-Pyridylmercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 210 from 6- (4-methanesulfonyloxy-butoxy) -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 2-mercapto-pyridine.

Melting point: 98-100 ° C.

Yield: 59.3% of theory.

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Example 214 6- [4- (4-Methyl-phenylmercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 210 from 5 6- (4-methanesulfonyloxy-butoxy) -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-methyl-thiophenol.

Melting point: 128-129 ° C.

Yield: 77.7% of theory.

Example 215 6- [4- (3,4-Dimethoxy-phenylmercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 210 from 6- (4-methanesulfonyloxy-butoxy) -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethoxy-thiophenol.

Melting point: 115-117 ° C.

Yield: 82.5% of theory.

Example 216 7- [4- (3,4-Dimethyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 210 from 7- (4-methanesulfonyloxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethyl-thiophenol.

Melting point: 120-122 ° C.

Yield: 84.5% of theory.

Example 217 7- [4- (4-Acetamido-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 210 from 7- (4-methanesulfonyloxy-butoxy) -4β-dimethyl-4H-3,1 -30-benzoxazin-2-one and 4-acetamido-thiophenol.

Melting point: 162-164 ° C.

Yield: 97.7% of theory.

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Example 218 7- [4- (2-Pyridylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 210 from 5- (4-methanesulfonyloxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 2-mercaptopyridine.

Melting point: 125-127 ° C.

Yield: 75.4% of theory.

Example 219 7- [4- (4-Methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 210 from 7- (4-methanesulfonyloxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-methyl-thiophenol.

Melting point: 120-122 ° C.

Yield: 80.7% of theory.

Example 220 7- [4- (4-Chloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 210 from 7- (4-methanesulfonyloxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-chloro-thiophenol.

Melting point: 117-119 ° C.

Yield: 86.7% of theory.

Example 221 7- [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 210 from 7- (4-methanesulfonyloxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dichloro-thiophenol.

Melting point: 104-106 ° C.

Yield: 79.7% of theory.

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Example 222 7- (4-Phenylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 210 from 5- (4-methanesulfonyloxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and thiophenol.

Melting point: 123-125 ° C.

Yield: 89.5% of theory.

Example 223 7- [4- (3,4-Dimethoxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 210 from 7- (4-methanesulfonyloxy-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethoxy-thiophenol.

Oil, RF value: 0.6 (silica gel plate: ethylene chloride / ethanol = 9: 1).

Yield: 80.7% of theory.

C22H27N05S (417.53)

calculated; C 63.29 H 6.52 N 3.35 Found; 63.00 6.54 3.38

Example 224 7- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 7- [4- (3,4-dichloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point; 8 ° -8 ° C.

Yield: 92.1% of theory.

Example 225 7- (4-Phenylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 7- (4-phenylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benz-oxazin-2-one and hydrogen peroxide.

Melting point: 117-119 ° C.

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Yield: 96.1% of theory.

Example 226 7- [4- (3,4-Dimethyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 7- [4- (3,4-dimethyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Oil, RF value: 0.6 (silica gel plate: ethylene chloride / ethanol = 9: 1).

Yield: 95.5% of theory.

C22H29N05S (419.54)

Calculated: C 62.98 H 6.97 N 3.35 S 7.64

Found: 63.24 6.85 3.40 7.64

Example 227 7- [4- (4-Acetamido-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 7- [4- (4-acetamido-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 145-147 ° C.

Yield: 77.8% of theory.

Example 228 7- [4- (2-Pyridylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 7- [4- (2-pyridylmercapto) butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 153-155 ° C.

Yield: 64.9% of theory.

Example 229 7- [4- (4-Methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 7- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-114

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3.1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 128-130 ° C.

Yield: 94.4% of theory.

Example 230 7- [4- (4-Chloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one.

Prepared analogously to Example 2 from 7- [4- (4-chloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3.1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 140-142 ° C.

Yield: 91.6% of theory.

Example 231 7- [4- (3,4-Dimethoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 7- [4- (3,4-dimethoxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Resin, RF value: 0.4 (silica gel plate: ethylene chloride / ethanol = 9: 1).

Yield: 40.8% of theory.

C22H27NO6S (433.53)

Calculated: C 60.95 H 6.28 N 3.23 S 7.40

Found: 60.70 6.25 3.03 7.53

Example 232 8- (4- (4-Cyclohexyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 8- [4- (4-cyclohexyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 144-145 ° C.

Yield: 71.9% of theory.

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Example 233 8- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 5 8- [4- (3,4-dichlorophenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point; 113-114 ° C.

Yield: 81.0% of theory.

Example 234 8- (4-Phenylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 8- (4-phenylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benz-oxazin-2-one and hydrogen peroxide.

Melting point: 162-163 ° C.

Yield: 91.6% of theory.

Example 235 8- [4- (4-Acetamido-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 8- [4- (4-acetamido-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 166-167 ° C.

Yield: 63.2% of theory.

Example 236 8- [4- (3,4-Dimethyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 8- [4- (3,4-dimethyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 111-112 ° C.

Yield: 63.9% of theory.

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Example 237 8- [4- (3,4-Dimethoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 5 8- [4- (3,4-Dimethoxy-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 102-103 ° C.

Yield: 90.2% of theory.

Example 238 6- [4- (4-Cyclohexyl-phenylsulfinyl) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-cyclohexyl-phenylmercapto) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 168-170 ° C.

Yield: 82.7% of theory.

Example 239 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (3,4-dichloro-phenylmercapto) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point. 91-93 ° C.

Yield: 70.9% of theory.

Example 240 6- (4-Phenylsulfinyl-butoxy) -4,4-diethyl-4H-3,1-benz-oxazin-2-one.

Prepared analogously to Example 2 from 6- (4-phenylmercapto-butoxy) -4,4-diethyl-4H-3,1-benz-oxazin-2-one and hydrogen peroxide.

Resin, RF value: 0.6 (silica gel plate: chloroform / ethanol = 9: 1).

Yield: 94.3% of theory.

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C22H27NO4S (401.53)

Calculated: C 65.81 H 6.78 N 3.49 S 7.98

Pound: 65.55 6.75 3.40 7.71

Example 241 6- [4- (3,4-Dimethyl-phenylsulfinyl) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (3,4-dimethyl-phenylmercapto) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 137-138 ° C.

Yield: 83.1% of theory.

Example 242 6- [4- (3,4-Dimethoxy-phenylsulfinyl) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (3,4-dimethoxy-phenylmercapto) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 161-163 ° C.

Yield: 87.7% of theory.

Example 243 6- [4- (4-Acetamido-phenylsulfinyl) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-acetamido-phenylmercapto) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 69-70 ° C.

Yield: 92.6% of theory.

Example 244 6- [4- (4-Pyridylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-pyridylmercapto) butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 141-143 ° C.

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Yield: 36.9% of theory.

Example 245 6- [4- (4,6-Dimethyl-2-pyrimidinylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4,6-dimethyl-2-pyrimidinylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Resin, RF value: 0.4 (silica gel plate: ethylene chloride / ethanol = 9: 1).

Yield: 15.0% of theory.

C20H25N3 ° 4S (403.50)

Calculated: C 59.53 H 6.25 S 7.95

Found: 59.30 5.99 7.88

Example 246 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4-methyl-4H-3.1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (3,4-dichloro-phenylmercapto) -butoxy] -4-methyl-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 138-139 ° C.

Yield: 86.0% of theory.

Example 247 6- [4- (4-Methyl-phenylsulfinyl) -butoxy] -4-methyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-methyl-phenylmercapto) -butoxy] -4-methyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide ·

Melting point: 120-121 ° C.

Yield: 58.4% of theory.

Example 248 6- [4- (4-Acetamido-phenylsulfinyl) -butoxy) -4-methyl-4H-3.1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-acetamido-phenylmercapto) -butoxy] -4-methyl-4H-119

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3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 124-126 ° C.

Yield: 60.4% of theory.

Example 249 5- [4- (2-Benzthiazolylsulfonyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 3 from 6- [4- (2-benzthiazolylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide / glacial acetic acid.

Melting point: 177-179 ° C.

Yield: 55.9% of theory.

Example 250 6- [4- (1,2,4-Triazolyl-3-sulfonyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 3 from 6- [4- (1,2,4-triazolyl-3-mercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide glacial acetic acid. Melting point: 197-199 ° C.

Yield: 83.0% of theory.

Example 251 6- [4- (2-Pyrimudinylsulfonyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 3 from 6- [4- (2-pyrimidinylmercapto) -butoxy] -4,4-dimethyl-4H-25,1-benzoxazin-2-one and hydrogen peroxide / glacial acetic acid.

Melting point: 184-186 ° C.

Yield: 69.0% of theory.

Example 252 5- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 5-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-phenylsulfinyl) -butyl bromide.

Melting point: 89-90 ° C.

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Yield: 73.2% of theory.

Example 253 5- [4- (3,4-Dichloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 5- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetate hydroxamic acid ethyl ester.

Melting point: 127-128 ° C.

Yield: 50% of theory.

Example 254 7- [4- (3,4-Dichloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 7- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetate hydroxamic acid ethyl ester.

Resin, RF value: 0.4 (silica gel plate: ethylene chloride / ethanol = 9: 1).

Yield: 39.2% of theory.

C20H22C12N4S (457.39)

Calculated: C 52.52 H 4.85 Cl 15.50 N 6.12 S 7.01

Found: 52.34 4.80 15.50 6.16 S 7.01

Example 255 7- [4- (3,4-Dimethyl-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 7- [4- (3,4-dimethyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-2-one acet-hydroxamic acid ethyl ester.

Melting point: 161-163 ° C.

Yield: 77.2% of theory.

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Example 256 7- [4- (4-Acetamido-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 5- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one ethyl ester.

Melting point: 197-198 ° C.

Yield: 29.2% of theory.

Example 257 7- [4- (4-Methyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 7- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acet hydroxamic acid. ethyl ester.

Melting point: 122-124 ° C.

Yield: 54.6% of theory.

Example 258 20 7- [4- (4-Chloro-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 7- [4- (4-chloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid ethyl ester.

Melting point: 103-105 ° C.

Yield: 53.8% of theory.

Example 259 7- (4-Phenylsulfoxymino-butoxy) -4,4-dimethyl-4H-3, Ι-ΒΟ benzoxazin-2-one.

Prepared analogously to Example 6 from 7- (4-phenylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benz-oxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid ethyl ester.

Melting point: 130-132 ° C.

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Yield: 75.1% of theory.

Example 260 7- [4- (3,4-Dimethoxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 7- [4- (3,4-dimethoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl hydroxamic acid-acetic acid ethyl ester.

Melting point: 110-112 ° C.

Yield: 81.2% of theory.

Example 261 8- [4- (4-Cyclohexyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 8- [4- (4-cyclohexyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetate hydroxamic acid ethyl ester.

Melting point: 115-116 ° C.

Yield: 47.9% of theory.

Example 262 8- [4- (3,4-Dimethyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 8- [4- (3,4-dimethyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl acethydroxamsyre acid ethyl ester;

Melting point: 130-131 ° C.

Yield: 89.6% of theory.

Example 263 8- [4- (3,4-Dichloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 8- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetate DK 16486U b hydroxamic acid ethyl ester.

Melting point: 144-145 ° C.

Yield: 59.6% of theory.

Example 264 8- (4-Phenylsulfoxymino-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 8- (4-phenylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benz-oxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid ethyl ester.

Melting point: 103-104 ° C.

Yield: 60% of theory.

Example 265 8- [4- (3,4-Dimethoxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 8- [4- (3,4-dimethoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetyl hydroxamic acid ethyl ester.

Melting point: 120-121 ° C.

Yield: 74.3% of theory.

Example 266 8- [4- (4-Acetamido-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 8- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetyl-hydroxamic acid. ethyl ester.

Melting point: 166-167 ° C.

Yield: 56.6% of theory.

Example 267 6- [4- (3,4-Dimethyl-phenylsulfoximino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 124

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6- [4- (3,4-Dimethyl-phenylsulfinyl) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acet-hydroxamic acid ethyl ester.

Melting point: 104-105 ° C.

Yield: 52.7% of theory.

Example 268 6- [4- (3,4-Dimethoxy-phenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (3,4-dimethoxy-phenylsulfinyl) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetate hydroxamic acid ethyl ester.

Melting point: 93-95 ° C.

Yield: 36.9% of theory.

Example 269 6- [4- (4-Cyclohexyl-phenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-cyclohexyl-phenylsulfinyl) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetyl-hydroxamic acid. ethyl ester.

Melting point: 158-160 ° C.

Yield: 36.6% of theory.

Example 270 6- [4- (4-Acetamide phenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acet-hydroxamic acid ethyl ester.

Melting point: 144-146 ° C.

Yield: 64.0% of theory.

UIV IOH-OOV D

125

Example 271 6- [4- (3,4-Dichloro-phenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 5- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetate hydroxamic acid ethyl ester.

Melting point: 136-138 ° C.

Yield: 68.7% of theory.

Example 272 6- (4-Phenylsulfoxymino-butoxy) -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- (4-phenylsulfinyl-butoxy) -4,4-diethyl-4H-3,1-benz-oxazin-2-one and O-mesitylenesulfonyl-acethydroxamic acid ethyl ester.

Melting point: 134-135 ° C.

Yield: 69.6% of theory.

Example 273 6- [4- (3,4-Dichloro-phenylsulfoxymino) -butoxy] -4-methyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4-methyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid ethyl ester.

Melting point: 179-180 ° C.

Yield: 67.6% of theory.

Example 274 6- [4- (4-Methyl-phenylsulfoxymino) -butoxy] -4-methyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4-methyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetydroxamic acid ethyl ester.

Melting point: 121-123 ° C.

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Yield: 45.5% of theory.

Example 275 6- [4- (4-Acetamido-phenylsulfoxymino) -butoxy] -4-methyl-4H-3,1-benzoxazin-2-one.

5 Prepared analogously to Example 6 from 6- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4-methyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid ethyl ester.

Melting point: 123-125 ° C.

Yield: 45.2% of theory.

Example 276 7- [4- (3,4-Dimethyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 7- [4- (3,4-dimethyl-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

island

Melting point: 151-153 ° C.

Yield: 70.0% of theory.

Example 277 20 7- [4- (4-Acetamido-N-acetyl-phenylsulfoxymino) -butoxy].

4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 7- [4-acetamido-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 136-138 ° C.

Yield: 38.8% of theory.

Example 278 7- [4- (4-Methyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 7- [4- (4-methyl-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 142-144 ° C.

Yield: 50.7% of theory.

127

Example 279 7- [4- (4-Chloro-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 5 7- [4- (4-chloro-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 127-129 ° C.

Yield: 85.0% of theory.

Example 280 7- [4- (3,4-Dichloro-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 7- [4- (3,4-dichloro-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 130-132 ° C.

Yield: 95.6% of theory.

Example 281 7- [4- (N-Acetyl-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 7- (4-phenylsulfoxymino-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 123-125 ° C.

Yield: 84.3% of theory.

Example 282 7- [4- (3,4-Dimethoxy-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 7- [4- (3,4-dimethoxy-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride. Melting point: 202-204 ° C.

Yield: 82.5% of theory.

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Example 283 8- [4- (4-Cyclohexyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 5 8- [4- (4-cyclohexyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 167-168 ° C.

Yield: 92.9% of theory.

Example 284 8- [4- (3,4-Dichloro-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 8- [4- (3,4-dichloro-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 170-171 ° C.

Yield: 100% of theory.

Example 285 8- [4- (3,4-Dimethyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 8- [4- (3,4-dimethyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 145-146 ° C.

Yield: 93.9% of theory.

Example 286 8- [- (N-Acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 8- (4-phenylsulfoxymino-butoxy) -4,4-dimethyl-4H-3,1 -30-benzoxazin-2-one and acetanhydride.

Melting point: 113-114 ° C.

Yield: 75.6% of theory.

UIV ΐο ^ οου d 129

Example 287 8- [4- (3,4-Dimethoxy-N-acetyl-phenyls-ulfoximino) -butox] - 4.4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 5 8- [4- (3,4-dimethoxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 137-138 ° C.

Yield: 90.2% of theory.

Example 288 8- [4- (4-Acetamido-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 8- [4- (4-acetamido-phenylsulfoximino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 183-184 ° C.

Yield: 88.6% of theory.

Example 289 6- [4- (4-Cyclohexyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (4-cyclohexyl-phenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 176-178 ° C.

Yield: 87.3% of theory.

Example 290 6- [4- (3,4-Dimethyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (3,4-dimethyl-phenylsulfoximino) -butoxy] -4,4-30-diethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Resin, RF value: 0.52 (silica gel plate: chloroform / ethanol = 9: 1).

Yield: 87.7% of theory.

C26H34N2 ° 5S (486'64> 35 Calculated: C 64.17 H 7.04 N 5.76 S 6.59

Found: 63.90 6.90 5.51 6.94 130

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Example 291 6- [4- (4-Acetamido-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 5 6- [4- (4-acetamido-pbenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 146-149 ° C.

Yield: 88.6% of theory.

Example 292 6- [4- (3,4-Dimethoxy-N-acetyl-phenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (3,4-dimethoxy-phenylsulfoximino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Resin, RF value: 0.5 (silica gel plate: chloroform / ethanol = 9: 1).

Yield: 87.2% of theory.

C26H34N2 ° 7S (518.64)

Calculated: C 60.21 H 6.61 N 5.40 6.18 Found: 59.95 6.58 5.19 6.31

Example 293 6- [4- (3,4-Dichloro-N-acetyl-phenylsulfoximino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 43 from 6- [4- (3,4-dichloro-phenylsulfoximino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 164-166 ° C.

Yield: 86.6% of theory.

Example 294 6- [4- (N-Acetyl-phenylsulfoxymino) -butoxy] -4,4-diethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- (4-phenylsulfoxymino-butoxy-4,4-diethyl-4H-3,1-benz-oxazin-2-one and acetanhydride.

Melting point: 120-122 ° C.

131

Yield: 89.4% of theory.

Example 295 6- [4- (3,4-Dichloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-phenylsulfoximino) -butyl bromide mesitylsulfonyl (m.p. 170-173 ° C).

Melting point: 164-166 ° C.

Yield: 35.4% of theory.

Example 296 6- [4- (3,4-Dichloro-N-acetul-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-N-acetyl-phenylsulfoximino) -butyl bromide (m.p. 78-79 ° C).

Melting point: 156-158 ° C.

Yield: 66.5% of theory.

Example 297 6- (4-Phenylsulfinyl-butoxy) -4H-3,1-benzoxazin-2-one.

4.2 g (0.0133 mole) of 2-amino-5- (4-phenylsulfinyl-butoxy) -benzyl alcohol (prepared from 2-nitro-5- (4-phenylsulfinyl-butoxy) -benzyl alcohol by catalytic hydrogenation) were dissolved. in 150 ml of chloroform and 6.5 g (0.05 mol) of potassium carbonate were added. To this mixture was slowly added, with stirring, 10 ml of 20% solution of phosgene in toluene. After 2 hours of stirring, the solution was washed with water, dried over sodium sulfate and the solvent was distilled off in vacuo.

The residue was recrystallized from acetic acid ethyl ester / cyclohexane.

Melting point: 115-116 ° C.

Yield: 2.1 g (45.8% of theory).

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Example 298 7- (4-Phenylsulfoxymino-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Potassium hydroxide (1.56 g) (2.78 mmol) was dissolved in methanol (10 ml) and stirred at room temperature with 0.8 g (1.86 mmol) of 7- [4- (N-acetyl-phenylsulfoximino) -butoxy ] -4,4-dimethyl-4H-3, l-benzoxazin-2-one. The resulting clear solution was left to stand overnight, then added to water, suction precipitated, washed with water and diisopropyl ether and dried at 60 ° C.

Melting point: 130-132 ° C.

Yield: 0.65 g (90% of theory).

Example 299 7,8-Dibromo-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 7,8-dibromo-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (4-methyl-phenylmercapto) -butyl chloride.

Melting point: 114-115 ° C.

Yield: 45.4% of theory.

Example 300 6- (4-Phenylsulfinyl-butoxy) -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 6-hydroxy-4,4,7-trimethyl-4H-3,1-benzoxazin-2-one and 4-phenylsulfinyl-butyl bromide.

Melting point: 124-125 ° C.

Yield: 51.6% of theory.

urv id ^ ouv u 133

Example 301 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 5 6-hydroxy-4,4,7-trimethyl-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-phenylsulfonyl) -butyl bromide.

Melting point: 151-152 ° C.

Yield: 42.3% of theory.

Example 302 6- [4- (4-Methyl-phenylmercapto) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and 4-methylthiophenol.

Melting point: 125-126 ° C.

Yield: 78.4% of theory.

Example 303 6- [4- (3,4-Dichloro-phenylmercapto) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4,8-trimethyl-4H-3,1-benzoxazine-2-and and 3,4-dichloro-thiophenol.

Melting point: 136-137 ° C.

Yield: 68.8% of theory.

Example 304 6- [4- (4-Acetamido-phenylmercapto) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4,8-trimethyl-4H-3,1-benzoxazine-2-30 one and 4-acetamido-thiophenol.

Melting point: 167-168 ° C.

Yield: 64.2% of theory.

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Example 305 6- [4- (2-Pyridylmercapto) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and 2-mercapto-pyridine.

Melting point: 144-145 ° C.

Yield: 64.0% of theory.

Example 306 6- [4- (4-Chloro-phenylmercapto) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and 4-chloro-thiophenol.

Melting point: 141-142 ° C.

Yield: 63.5% of theory.

Example 307 6- (4-Phenylmercapto-butoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and thiophenol.

Melting point: 125-126 ° C.

Yield: 83.1% of theory.

Example 308 6- [4- (3,4-Dimethyl-phenylmercapto) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 1 from 6- (4-chlorobutoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethyl-thiophenol.

Melting point: 146-147 ° C.

Yield: 78.1% of theory.

135

Example 309 6- [4- (3,4-Dimethoxy-phenylmercapto) -butoxy] -4,4,8-trimethyl-4H-1,3-benzoxazin-2-one.

Prepared analogously to Example 1 from 5 6- (4-chlorobutoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and 3,4-dimethoxy-thiophenol.

Melting point: 130-131 ° C.

Yield: 73.3% of theory.

Example 310 6- [4- (4-Acetamido-phenylsulfinyl) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-acetamido-phenylmercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 240-241 ° C.

Yield: 72.6% of theory.

Example 311 6- [4- (4-Chloro-phenylsulfinyl) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-chloro-phenylmercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 159-160 ° C.

Yield: 83.4% of theory.

Example 312 6- [4- (2-Pyridylsulfinyl) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (2-pyridylmercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 156-157 ° C.

Yield: 69.1% of theory.

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Example 313 6- [4- (4-Methyl-phenylsulfinyl) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 5 6- [4- (4-methyl-phenylmercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 176-177 ° C.

Yield: 76.1% of theory.

Example 314 6- [4- (3,4-Dimethoxy-phenylsulfinyl) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (3,4-dimethoxy-phenylmercapto) -butoxy] -7-nitro-4,4-dimethyl-3H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 190-192 ° C.

Yield: 84.3% of theory.

Example 315 6- [4- (3,4-Dimethyl-phenylsulfinyl) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (3,4-dimethyl-phenylmercapto) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 146-147 ° C.

Yield: 68.2% of theory.

Example 316 8-Chloro-6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 8-chloro-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 113-114 ° C.

Yield: 90.3% of theory.

137

Example 317 7- Chloro-6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 5 7-chloro-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 143-144 ° C.

Yield: 85.3% of theory.

Example 318 6- [4- (4-Chloro-phenylsulfinyl) -butoxy] -8-chloro-4,4-dimethyl-4H-3,1-benzoxazine-2-oη.

Prepared analogously to Example 2 from 8- chloro-6- [4- (4-chloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 83-85 ° C.

Yield: 78.1% of theory.

Example 319 6- [4- (4-Chloro-phenylsulfinyl) -butoxy] -7-chloro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 7- chloro-6- [4- (4-chloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 162-163 ° C.

Yield: 86% of theory.

Example 320 7-Bromo-6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 7-bromo-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 143-145 ° C.

Yield: 78.5% of theory.

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Example 321 8-Bromo-6- [4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 5 8-bromo-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 123-124 ° C.

Yield: 86.4% of theory.

Example 322 6- [4- (4-Methyl-phenylsulfinyl) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 152-153 ° C.

Yield: 87.2% of theory.

Example 323 7.8- Dibromo-6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 7,8-dibromo-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 138-139 ° C.

Yield: 70.0% of theory.

Example 324 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (3,4-dichloro-phenylmercapto) -butoxy] -4,4,8-tri-methyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 158 ° C.

Yield: 68% of theory.

139

Example 325 6- [4- (4-Methyl-phenylsulfinyl) -butoxy-4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 5 6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 137-138 ° C.

Yield: 40% of theory.

Example 326 6- [4- (4-Chloro-phenylsulfinyl) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-chloro-phenylmercapto) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 163-164 ° C.

Yield: 66.2% of theory.

Example 327 6- [4- (3,4-Dimethoxy-phenylsulfinyl) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (3,4-dimethoxy-phenylmercapto) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 142-143 ° C.

Yield: 70.5% of theory.

Example 328 6- [4- (3,4-Dimethyl-phenylsulfinyl) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (3,4-dimethyl-phenylmercapto) -butoxy] -4,4,8-tri-methyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 113-114 ° C.

Yield: 72.9% of theory.

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Example 329 6- (4-Phenylsulfinyl-butoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 5 6- (4-phenylmercapto-butoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 143-144 ° C.

Yield: 77.6% of theory.

Example 330 6- [4- (4-Acetamido-phenylsulfinyl) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-acetamido-phenylmercapto) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 212-213 ° C.

Yield: 57.9% of theory.

Example 331 6- [4- (2-Pyridylsulfinyl) -butoxy] -4,4,8-trimethyl-4H-3.1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (2-pyridylmercapto) butoxy] -4,4,8-trimethyl-4H-3.1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 163-164 ° C.

Yield: 65.8% of theory.

Example 332 6- [4- (3,4-Dimethoxy-phenylsulfoxymino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (3,4-dimethoxy-phenylsulfinyl) -butoxy] -4,4,8-tri-methyl-4H-3,1-benzoxazin-2-one and O- mesitylenesulfonyl-acethydroxamsyre acid ethyl ester.

Melting point: 175-176 ° C.

Yield: 58.7% of theory.

141

Example 333 6- [4- (3,4-Dimethyl-phenylsulfoxymino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 5- [4- (3,4-dimethyl-phenylsulfinyl) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and 0 -mesitylensulfonyl-acethydroxamsyre acid ethyl ester.

Melting point: 174-175 ° C.

Yield: 61.8% of theory.

Example 334 6- (4-Phenylsulfoxymino-butoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- (4-phenylsulfinyl-butoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydrazamic acid ethyl ester.

Melting point: 147-148 ° C.

Yield: 66.8% of theory.

Example 335 6- [4- (3,4-Dichloro-phenylsulfoximino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4,8-tri-methyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl -25 acetyl hydroxamic acid ethyl ester.

Melting point: 116-117 ° C.

Yield: 50.0% of theory.

Example 336 6- [4- (4-Chloro-phenylsulfoxymino) -butoxy] -4,4,8-tri-methyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-chloro-phenylsulfinyl) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetyl hydroxamic acid ethyl ester.

Melting point: 167-168 ° C.

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Yield: 72.8% of theory.

Example 337 6- [4- (4-Methyl-phenylsulfoxymino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-methyl-phenylsulfinyl) -butoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetate hydroxamic acid ethyl ester.

Melting point: 183-184 ° C.

Yield: 71.5% of theory.

Example 338 6- [4-Acetamido-phenylsulfoxymino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazone-2-one and O-mesitylene sulfonyl acethydroxamsyre acid ethyl ester.

Melting point: 168-169 ° C.

Yield: 66.1% of theory.

Example 339 6- [4- (4-Acetamido-phenylsulfoxymino) -butoxy] -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl acethydroxamsyre acid ethyl ester.

Melting point: 209-211 ° C.

Yield: 55.4% of theory.

Example 340 6- [4- (4-Chloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-chloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-143 acethydroxamsyre acid ethyl ester.

Melting point: 116-118 ° C.

Yield: 88.3% of theory.

Example 341 6- [4- (4-Methyl-phenylsulfoximino) -butoxy] -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-10 acethydroxamsyre acid ethyl ester.

Melting point: 112-114 ° C.

Yield: 86.2% of theory.

Example 342 6- [4- (3,4-Dimethoxy-phenylsulfoxymino) -butoxy] -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (3,4-dimethoxy-phenylsulfinyl) -butoxy] -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one and 0 -mesitylensul-fony1-acethydroxamsyre acid ethyl ester.

Melting point: 147-149 ° C.

Yield: 41.4% of theory.

Example 343 6- [4- (3,4-Dimethyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (3,4-dimethyl-phenylsulfinyl) -butoxy] -4-4-dimethyl-7-nitro-4H-3,1-benzoxazin-2-one and mesitylensul-O-sulfonyl-acethydroxamsyre acid ethyl ester.

Melting point: 145-146 ° C.

Yield: 67% of theory.

Example 344 8-Chloro-6- [4- (3,4-dichloro-phenylsuccoximino) -butoxy] -4,4-dimethyl-4H-1,3-benzoxazin-2-one.

Prepared analogously to Example 6 from 144

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8-Chloro-6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonylacethydroxamic acid ethyl ester.

Melting point: 135-136 ° C.

Yield: 74.3% of theory.

Example 345 7- Chloro-6- [4- (3,4-dichloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 7-Chloro-6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O- mesitylenesulfonyl-acethydroxamsyre acid ethyl ester.

Melting point: at 87 ° C.

Yield: 58.3% of theory.

Example 346 8- Chloro-6- [4- (4-methyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 8-chloro-6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl acethydroxamsyre acid ethyl ester.

Melting point: 132-133 ° C.

Yield: 55.1% of theory.

Example 347 7-Chloro-6- [4- (4-methyl-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 7-chloro-6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-3 0 acetyl hydroxamic acid ethyl ester.

Melting point: 115-116 ° C.

Yield: 55.1% of theory.

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Example 348 8-Chloro-6- [4- (4-chloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 5 8-chloro-6- [4- (4-chloro-phenylsulfonyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl acethydroxamsyre acid ethyl ester.

Melting point: 162-163 ° C.

Yield: 57% of theory.

Example 349 7-Chloro-6- [4- (4-chloro-phenylsulfoxymino) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 7-chloro-6- [4- (4-chloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and O- mesitylenesulfonyl-acethydroxamsyre acid ethyl ester.

Melting point: 132-133 ° C.

Yield: 65.8% of theory.

Example 350 6- [4- (3,4-Dichloro-phenylsulfoximino) -butoxy] -4,4,7-trimethyl-4K-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl -acet-hydroxamic acid ethyl ester.

Melting point: 135-137 ° C.

Yield: 63.6% of theory.

Example 351 6- (4-Phenylsulfoxymino-butoxy) -4,4,7-trimethyl-4H-3,1-30-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- (4-phenylsulfinyl-butoxy) -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acethydroxamic acid ethyl ester.

Melting point: 123-124 ° C.

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Yield: 77% of theory.

Example 352 6- [4- (4-Methyl-phenylsulfoxymino) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 6 from 6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl-acetate hydroxamic acid ethyl ester.

Melting point: 153-154 ° C.

Yield: 57.6% of theory.

Example 353 6- [- (4-Acetamido-N-acetyl-phenylsulfoxymino) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (4-acetamido-phenylsulfoxymino) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride. Melting point: 250-252 ° C.

Yield: 92% of theory.

Example 354 6- [4- (4-Chloro-N-acetyl-phenylsulfoxymino) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (4-chloro-phenylsulfoximino) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 211-213 ° C.

Yield: 82.4% of theory.

Example 355 6- [4- (4-Methyl-N-acetyl-phenylsulfoxymino) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (4-methyl-phenylsulfoximino) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 214-216 ° C.

Yield: 85.8% of theory.

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Example 356 6- [4- (3,4-Dimethoxy-N-acetyl-phenylsulfoxymino) -butoxy] -7-nitro-4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 5 6- [4- (3,4-dimethoxy-phenylsulfoxymino) -butoxy] -7-nitro-4,4-dimethyl-4H-3fl-benzoxazin-2-one and acetanhydride. Melting point: 120-122 ° C.

Yield: 82.2% of theory.

Example 357 6- [4- (3,4-Dimethoxy-N-acetyl-phenylsulfoxymino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (3,4-dimethoxy-phenylsulfoxymino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 123-124 ° C.

Yield: 76.5% of theory.

Example 358 6- [4- (3,4-Dimethyl-N-acetyl-phenylsulfoxymino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (3,4-dimethyl-phenylsulfoximino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and acetanhydride. Melting point: 146-147 ° C.

Yield: 83.1% of theory.

Example 359 6- [4- (N-Acetyl-phenylsulfoxymino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 43 from 6- (4-phenylsulfoxymino-butoxy) -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 99-100 ° C.

Yield: 71.0% of theory.

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Example 360 6- [4- (3,4-Dichloro-N-acetyl-phenylsulfoximino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 5- [4- (3,4-dichloro-phenylsulfoxymino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point; 140-141 ° C.

Yield; 76.9% of theory.

Example 361 6- [4- (4-Chloro-N-acetyl-phenylsulfoxymino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 143 from 6- [4- (4-chloro-phenylsulfoximino) -butoxy] -4,4,8-trimethyl-4H-3,1-benzoxazin-2-one and acetanhydride.

Melting point: 178-179 ° C.

Yield; 79.9% of theory.

Example 362 8-Chloro-6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 8-chloro-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-phenylsulfinyl) -butyl bromide.

Melting point: 121-122 ° C.

Yield: 62.0% of theory.

Example 363 7- Chloro-6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 7-chloro-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 4- (3,4-dichloro-phenylsulfinyl) -butyl bromide.

Melting point: 125-127 ° C.

Yield: 41.5% of theory.

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Example 364 8-Chloro-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 5 8-chloro-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (4-methyl-phenylmercapto) -butyl chloride. Melting point; 111-112 ° C.

Yield; 56.0% of theory.

Example 365 8-Chloro-6- (4-phenylsulfinyl-butoxy) -4,4-dimethyl-4H-3.1-benzoxazin-2-one.

Prepared analogously to Example 4 from 8-chloro-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-phenylsulfinyl-butyl bromide.

Melting point; 154-155 ° C.

Yield; 39.3% of theory.

Example 366 7-Chloro-6- (4-phenylsulfonyl-butoxy) -4,4-dimethyl-4H-3.1-benzoxazin-2-one.

Prepared analogously to Example 4 from 7-chloro-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-phenylsulfinyl-butyl bromide.

Melting point; 124-125 ° C.

Yield: 31.5% of theory.

Example 367 7-Chloro-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 7-chloro-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 4- (4-methyl-phenylmercapto) -butyl chloride. Melting point: 118-119 ° C.

Yield: 52.6% of theory.

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Example 368 7-Bromo-6- [4- (3,4-dichloro-phenylsulfonyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 5 7-bromo-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (3,4-dichloro-phenylsulfinyl) -butyl bromide.

Melting point: 136-138 ° C.

Yield: 75.0% of theory.

Example 369 10 7-Bromo-6- (4-phenylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 7- bromo-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-phenylsulfinyl-butyl bromide.

Melting point: 119-120 ° C.

Yield: 53.1% of theory.

Example 370 8- Chloro-6- [4- (4-chloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 8-chloro-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (4-chloro-phenylmercapto) -butyl chloride.

Melting point: 138-139 ° C.

Yield: 56.7% of theory.

Example 371 8-Bromo-6- [4- (3,4-dichloro-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 8-bromo-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 4- (3,4-dichloro-phenylsulfinyl) -butyl bromide.

Melting point: 74 ° C.

Yield: 82.5% of theory.

υιν i dhoou d 151

Example 372 8-Bromo-6- (4-phenylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 5 8-bromo-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-phenylsulfinyl-butyl bromide.

Melting point: 129-130 ° C.

Yield: 41.1% of theory.

Example 373 10 7-Chloro-6- [4- (4-chloro-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 7-chloro-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (4-chloro-phenylmercapto) -butyl chloride.

Melting point: 125-126 ° C.

Yield: 45.2% of theory.

Example 374 6- [4- (4-Methyl-phenylmercapto) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 6- hydroxy-4,4,7-trimethyl-4H-3,1-benzoxazin-2-one and 4- (4-methyl-phenylmercapto) -butyl chloride.

Melting point: 114-115 ° C.

Yield: 51.9% of theory.

Example 375 7- Bromo-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 7-bromo-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one 30 and 4- (4-methyl-phenylmercapto) -butyl chloride.

Melting point: 122-123 ° C.

Yield: 43.3% of theory.

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Example 376 8-Bromo-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 5 8-bromo-6-hydroxy-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4- (4-methyl-phenylmercapto) -butyl chloride.

Melting point: 115-116 ° C.

Yield: 43.3% of theory.

Example 377 10 8-Chloro-6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 8-chloro-6- [4- (4-methyl-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 114-115 ° C.

Yield: 72.7% of theory.

Example 378 6- [4- (4-Acetamido-phenylsulfinyl) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-acetamido-phenylmercapto) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 210-211 ° C.

Yield: 70.6% of theory.

Example 379 6- [4- (4-Methyl-phenylsulfinyl) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 152-153 ° C.

Yield: 87.2% of theory.

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Example 380 8-Chloro-6- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 5 8-chloro-6- [4- (4-acetamido-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 130-132 ° C.

Yield: 85.0% of theory.

Example 381 10 5,7-Dimethyl-6- [4- (4-methyl-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 5,7-dimethyl-6-hydroxy-4H-3,1-benzoxazin-2-one and 4- (4-methyl-phenylmercapto) -butyl chloride.

Melting point: 107-109 ° C.

Yield: 28.3% of theory.

Example 382 6- [4- (4-Methyl-phenylsulfinyl) -butoxy] -5,7-dimethyl-4H-3.1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- [4- (4-methyl-phenylmercapto) -butoxy] -5,7-dimethyl-4H-3.1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 114-116 ° C.

Yield: 52.6% of theory.

Example 383 6- [4- (3,4-Dichloro-phenylsulfinyl) -butoxy] -5,7-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 6- (4- (3,4-dichloro-phenylmercapto) -butoxy] -5,7-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 126-128 ° C.

Yield: 39.8% of theory.

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Example 384 7-Chloro-6- [4- (4-methyl-phenylsufinyl) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 5 7-chloro-6- [4- (4-methyl-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 177-178 ° C.

Yield: 72.0% of theory.

Example 385 10 5-Chloro-6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 5-chloro-6- [4- (4-methyl-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 183-185 ° C.

Yield: 20.6% of theory.

Example 386 5.7- Dichloro-6- [4- (4-methyl-phenylsulfinyl) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 5.7-dichloro-6- [4- (4-methyl-phenylmercapto) -butoxy] -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide. Melting point: 169-170 ° C.

Yield: 75.0% of theory.

Example 387 5.7- Dichloro-6- (4-phenylsulfinyl-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 2 from 5.7-dichloro-6- (4-phenylmercapto-butoxy) -4,4-dimethyl-4H-3,1-benzoxazin-2-one and hydrogen peroxide.

Melting point: 186-187 ° C.

Yield: 74.0% of theory.

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Example 388 6- [4- (4-Acetamido-phenylmercapto) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 5 6-hydroxy-4,4,7-trimethyl-4H-3,1-benzoxazin-2-one and 4- (acetamido-phenylmercapto) -butyl mesylate.

Melting point: 104-106 ° C.

Yield: 50.9% of theory.

Example 389 10 7-Chloro-6- [4- (4-methyl-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 7- Chloro-6-hydroxy-4H ~ 3,1-benzoxazin-2-one and 4- (4-methyl-phenylmercapto) -butyl chloride.

Melting point: 145-147 ° C.

Yield: 44% of theory.

Example 390 7-CHloro-6- (4-phenylsulfinyl-butoxy) -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 7-chloro-6-hydroxy-4H-3,1-benzoxazin-2-one and 4-phenylsulfinyl-butyl chloride.

Melting point: 177-179 ° C.

Yield: 18.1% of theory.

Example 391 5-Chloro-6- [4- (4-methyl-phenylmercapto) -butoxy] -4H-3,1-benzoxazin-2-one.

Prepared analogously to Example 4 from 5-chloro-6-hydroxy-4H-3,1-benzoxazin-2-one and 4- (4-methyl-30-phenylmercapto) -butyl chloride.

Melting point: 144-145 ° C.

Yield: 12.7% of theory.

Claims (13)

Example 393 6- [4- (4-Acetamido-phenylsulfoxymino) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one. Prepared analogously to Example 6 from 6- [4- (4-acetamido-phenylsulfinyl) -butoxy] -4,4,7-trimethyl-4H-3,1-benzoxazin-2-one and O-mesitylene sulfonyl -acethydroxamzyre acid ethyl ester. Melting point: 159-161 ° C. Yield: 53.3% of theory. 20 1. Analogous Process for the Preparation of Benzo-xazin-2-Ones of General Formula I R Ro R-s 25. In 0 R.-ADO - i ^ A,> ° R6 \ wherein 30. is a sulfur atom, a SO, SO2 ~, RN = S group or RN = SO group in which R is a hydrogen atom , a straight chain alkanoyl group having 1-9 carbon atoms, a pivaloyl group, a benzoyl group optionally substituted with a fluoro, chloro or bromine atom or with a methyl, ethyl, isopropyl, t-butyl or acetoxy group , a benzoyl group substituted with two fluorine atoms, two chlorine atoms or two or three methyl groups, , methanesulfonyl, ethanol sulfonyl, pentamethylphenylsulfonyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, benzyloxycarbonyl, amino carbonyl, methylaminocarbonyl or dimethylamino carbonyl group, 10. or with 2-6 carbon atoms, R 1 is optionally with a phenylgr substituted alkyl group substituted alkyl group having 1-3 carbon atoms or a phenyl group, the above-mentioned phenyl core being substituted in each case by an alkyl group having 1-4 carbon atoms, a halogen atom, an alkoxy group having 1-3 carbon atoms, a hydroxy -, cyclohexyl or phenyl group, an amino group or an alkanoylamino group having 1-3 carbon atoms; an alkyl group of 4-8 carbon atoms, a cycloalkyl group of 3-7 carbon atoms, one of alkyl groups of 1-4 carbon atoms, alkoxy groups of 1-3 carbon atoms and / or halogen atoms, di- or trisubstituted phenyl group or mono- or disubstituted hydroxyphenyl group. or aminophenyl group, wherein the substituents on the phenyl nucleus may in each case be the same or different, optionally substituted with one or two methyl groups, pyridyl or pyriminidyl group, a pyridyl-N-oxide, ethylpyridyl, ethylpyrimidinyl, propylpyrimidinyl, diethyl -, pyrazinyl, pyridazinyl, pyrazolyl, imidazolyl, triazolyl, indolyl, indazolyl, quinolyl, isoquinolyl, quinazolinyl, benzimidazolyl or benzthiazolyl group, R 2 and R 3, which may be the same or different, -35 atoms, phenyl groups, alkyl groups having 1 to 6 carbon atoms or cycloalkyl groups having 3 to 7 carbon atoms, R4 is a hydrogen atom or an alkyl group having 1 13 carbon atoms, R5 is a hydrogen or halogen atom, a nitro or alkyl group of 1 to 3 carbon atoms, and 5 R6 is a hydrogen or halogen atom or an alkyl group of 1 to 3 carbon atoms, characterized in that a) reacting a hydroxy compound of general formula II 10 PR vx- H0 'L o II 15 o' 6 * 4 wherein R2 to Rg are as previously defined, or salts thereof with inorganic or tertiary organic bases, with a compound of the general formula III Z - D - A - Ri III wherein A, D and R 1 are as previously defined and Z is a nucleophilic leaving group, or b) for the preparation of compounds of general formula I wherein A is an SO, SO 2 or RN = SO group oxidizes a compound of general formula IV 30. np RR ,. 35/1 p of R. R6 4 159 wherein R1 to Rg and D have the previous definitions and A 'is a sulfur atom, an SO or RN = S group wherein R is as previously defined, or c) for preparation of compounds of the general formula I wherein A is a sulfur atom or a SO 2 group: a compound of the general formula V R5 R2 R3 R6 Ht 15 ^ wherein D and R2 to R6 are defined as before and X is a nucleophilic leaving group having a compound of general formula VI Y - R 1 VI wherein R is defined as before and Y is a MeSO 2 'group, wherein Me is an alkali or alkaline earth / 2 metal atom or a mercapto group, or d) for the preparation of compounds of the general formula I, wherein A is an HN = SO group: a sulfoxide of the general formula VII 30 Ri - so - D - 0 -, in Lo VI1 · K wherein 35. and Ri to Rg are defined as before, with optionally formed nitrogen hydrogen acid in the reaction mixture, or DK 164860 B 160 e) for the preparation of compounds with the general Formula I wherein A is an HN = SO group: reactes a sulfoxide of general formula VII> ·, * y '' R, 'OR 10 4 wherein D and R 1 to R 9 are defined as before, with a compound having the general formula VIII H2N - O - X - r7 VIII wherein X is a carbonyl or sulfonyl group and is an o-position disubstituted aryl group, or f) to prepare a compound of general formula I wherein R is not a hydrogen atom: acylates a compound of the general formula IX TL KV ^ X! R -A "-D-0 - II IX hh 3q wherein D and R1 to Rg are as previously defined and A" is an HN = S or HN = SO group, or g) to prepare a compound of the general formula I wherein A is an RN = S group: 35 represents a thioether of the general formula X 161 "RR R.-SDC-- I Λ v 1 W \ 0 X 5 ^ R6 R 4 wherein R 1 to R 9 and D are as previously defined with a h-100 logenamide of the general formula XI Kai XI R 'N H wherein R ', other than a hydrogen atom, has the meanings previously mentioned and R is a chlorine or bromine atom and optionally subsequently hydrolyzes a compound thus obtained, or h) to prepare a compound of general formula I wherein A is an HN = S or HN = SO group: an acyl residue hydrolytically separates from a compound of general formula XII RR, H, ° * 6 H '4 wherein D and R 1 to R 5 are as previously defined, and A '' is a HN = S or HN = SO group substituted with a hydrolytically cleavable acyl residue, or i) to prepare a compound of general formula I wherein R is not a hydrogen atom: a compound of general formula XIII 5. R, R, / 3 5 C V \ y ^ oh xiii R -Α - Ε-0 - I g R4b wherein D and R1 to Rg are as previously defined and A "" is a sulfur atom, a SO-, SO2 ~, R'-N = S- or R'-N = SO-group, wherein R ', other than a hydrogen atom, have the meanings previously mentioned for R, with a carbonic acid derivative of the general formula XIV X - CO - X XIV wherein 20 may be the same or different, in each case a nucleophilic leaving group such as a chlorine atom, a methoxy, ethoxy, benzyloxyl or imidazolyl group, and if desired then transferring by alkylation a a compound of the general formula I obtained in which R 4 is a hydrogen atom in a corresponding compound of the general formula I wherein R 4 is an alkyl group having 1 to 3 carbon atoms.